Use of di-ionic compounds as corrosion inhibitors in a water system

ABSTRACT

Disclosed herein are the methods of using di-cationic or di-anionic compounds, which are derived from primary amine through an aza-Michael addition with an activated olefin, in a corrosion control composition to mitigate corrosion of a surface in a water system. The disclosed methods or compositions are found to be more effective than those methods or compositions including commonly used single quaternary compounds for mitigating corrosion for a metal surface in water systems.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority and relates to U.S. ProvisionalApplication Ser. No. 62/552,108, filed on Aug. 30, 2017 and entitled“MOLECULES HAVING ONE HYDROPHOBIC AND TWO IDENTICAL HYDROPHILIC GROUPSAND COMPOSITIONS THEREOF AND METHODS OF PREPARATION THEREOF.” The entirecontents of this patent application are hereby expressly incorporatedherein by reference including, without limitation, the specification,claims, and abstract, as well as any figures, tables, or drawingsthereof.

This application also relates to U.S. non-Provisional application Ser.No. 16/116,222, filed on Aug. 29, 2018 and titled “MOLECULES HAVING ONEHYDROPHOBIC GROUP AND TWO IDENTICAL HYDROPHILIC IONIC GROUPS ANDCOMPOSITIONS THEREOF AND METHODS OF PREPARATION THEREOF.” The entirecontents of this patent application are hereby expressly incorporatedherein by reference including, without limitation, the specification,claims, and abstract, as well as any figures, tables, or drawingsthereof.

FIELD OF THE INVENTION

The present disclosure relates generally to the field of corrosioncontrol in a water system. In particular, the present disclosure relatesto using a new class of compounds that comprise two identicalhydrophilic ionic groups and one hydrophobic group for inhibitingcorrosion in a water system. The compounds disclosed herein share somestructural features with conventional or Gemini surfactants but arestructurally distinguishable from the existing surfactants. Thecompounds disclosed herein are found to be effective corrosioninhibitors.

BACKGROUND OF THE INVENTION

Quaternary ammonium compounds comprise an important subcategory ofsurfactants because they contain unique properties. A main distinctionbetween quaternary ammonium compounds and other surfactants is theirunique structure. Quaternary ammonium compounds consist mainly of twomoieties, a hydrophobic group, e.g., long alkyl group, and a quaternaryammonium salt group. The unique positive charge of the ammonium plays akey role, e.g., electrostatic interactions, between the surfactant andsurface.

Industrial water systems employ process water to serve many differentpurposes but may be prone to microbial contamination and fouling. Metalsurfaces in any water system are prone to corrosion, partly due tomicrobial contamination and fouling.

Corrosion inhibitors are often added into a water system to protect itsmetal surfaces infrastructure, such as carbon steel pipelines, fromcorrosion. However, the quaternary ammonium compounds used for suchpurposes are often bis quaternary species or species quaternized withbenzyl chloride and are known to be very hazardous. In additional,governmental regulations exist to release any water containing singlequaternary compounds into the environment.

Therefore, there is a continuing need for different or alternativequaternary ammonium compounds that are better and safer corrosioncontrol agents.

Accordingly, it is an objective of the present disclosure to developnovel corrosion control agents having improved corrosion controlproperties.

It is a further objective of the disclosure to develop methods andcorrosion control compositions to make the corrosion in a water systemmore efficient and effective.

These and other objects, advantages and features of the presentdisclosure will become apparent from the following specification takenin conjunction with the claims set forth herein.

BRIEF SUMMARY OF THE INVENTION

Disclosed herein are the methods and compositions for corrosion controlfor a metal surface in a water system. Specifically, the disclosedmethods and compositions for corrosion control for a water system useone or more water soluble di-cationic or di-anionic compounds derivedfrom water soluble primary amines (Michael donor) by an aza-Michaeladdition reaction with an activated olefin (Michael acceptor).

The exemplary di-cationic or di-anionic compounds disclosed herein havea superior performance than the conventional single quaternary ammoniumcompounds used for mitigating corrosion for metal surfaces in watersystems. The exemplary di-cationic or di-anionic compounds disclosedherein also show improved performance when they are used as a foulingcontrol agent in a water system. Therefore, the disclosed corrosioncontrol compositions or methods have an advantage of not only preventingcorrosion of surfaces but also preventing microbial/biofilm growth,leading to overall reduction in chemical uses, cost, and operationcomplexity for operating a water system.

In one aspect, disclosed herein is a method for inhibiting corrosion ata surface in a water system, the method comprises providing a corrosioncontrol composition or a use solution of the corrosion controlcomposition into a water system to generate a treated water system oronto a surface of the water system, wherein the corrosion controlcomposition comprises one or more compounds according to one of FormulaI, Formula II, and Formula III and one or more additional corrosioncontrol composition agents,

wherein X is NH or O; R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is anunsubstituted or substituted, linear or branched C₅-C₃₀ alkyl, cyclicalkyl, alkenyl, or alkynyl group; Z is NH or O; R² is H, CH₃, or anunsubstituted, linear or branched C₂-C₁₀ alkyl, alkenyl, or alkynylgroup; m is an integer of 1 to 4; R³ is absent or an unsubstituted,linear C₁-C₃₀ alkylene group; Y is —N R⁴R⁵R⁶⁽⁺⁾; Y′ is —COOH, —SO₃H,—PO₃H, —OSO₃H, —OPO₃H, or a salt thereof; R⁴, R⁵, and R⁶ areindependently a C₁-C₁₀ alkyl group; R^(2′) is H, CH₃, or anunsubstituted or substituted, linear or branched C₁-C₁₀ alkyl, alkenyl,alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′, and wherein thecorrosion control composition mitigates corrosion on the surface in thewater system.

In other aspect, disclosed herein is a corrosion control composition,the corrosion control composition comprises one or more compoundsaccording to one of Formula I, Formula II, and Formula III and one ormore additional corrosion control composition agents,

wherein X is NH or O; R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is anunsubstituted or substituted, linear or branched C₅-C₃₀ alkyl, cyclicalkyl, alkenyl, or alkynyl group; Z is NH or O; R² is H, CH₃, or anunsubstituted, linear or branched C₂-C₁₀ alkyl, alkenyl, or alkynylgroup; m is an integer of 1 to 4; R³ is absent or an unsubstituted,linear C₁-C₃₀ alkylene group; Y is —N R⁴R⁵R⁶⁽⁺⁾; Y′ is —COOH, —SO₃H,—PO₃H, —OSO₃H, —OPO₃H, or a salt thereof; R⁴, R⁵, and R⁶ areindependently a C₁-C₁₀ alkyl group; R^(2′) is H, CH₃, or anunsubstituted or substituted, linear or branched C₁-C₁₀ alkyl, alkenyl,alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′, and wherein thecorrosion control composition mitigates corrosion on the surface in thewater system.

The forgoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodimentsand features described above, further aspects, embodiments, and featuresof the present technology will become apparent to those skilled in theart from the following drawings and the detailed description, whichshows and describes illustrative embodiments of the present technology.Accordingly, the figures and detailed description are also to beregarded as illustrative in nature and not in any way limiting.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A, FIG. 1B, and FIG. 1C shows a representation of an exemplarycompound of the disclosure (FIG. 1C), together with comparativerepresentations for a conventional surfactant (FIG. 1A) and Geminisurfactant (FIG. 1B).

FIG. 2 shows a generic reaction scheme between a primary amine andactivated olefin (α, β-unsaturated carbonyl compound) including acationic group.

FIG. 3 shows the corrosion rate in mils per year (mpy) during the bubbletest period (18 hour). For the blank sample, no 2-mercaptoethanol (2ME)was added.

Various embodiments of the present disclosure will be described indetail with reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the disclosure. Figuresrepresented herein are not limitations to the various embodimentsaccording to the disclosure and are presented for exemplary illustrationof the disclosure.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Disclosed herein are methods of using a new class of di-cationic ordi-anionic compounds for controlling corrosion on surfaces in a watersystem and corresponding corrosion control compositions comprising thisnew class of di-cationic or di-anionic compounds. Specifically, usingone or more di-cationic or di-anionic compounds, which comprise twoidentical hydrophilic groups and one hydrophobic group and are derivedfrom an aza-Michael addition reaction between a primary amine (Michaeldonor) and activated olefin (Michael acceptor), as corrosion controlagents are disclosed.

The embodiments of this disclosure are not limited to particularcompositions and methods of use which can vary and are understood byskilled artisans. It is further to be understood that all terminologyused herein is for describing particular embodiments only and is notintended to be limiting in any manner or scope. For example, as used inthis specification and the appended claims, the singular forms “a,” “an”and “the” can include plural referents unless the content clearlyindicates otherwise. Further, all units, prefixes, and symbols may bedenoted in its SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this disclosure are presented in a range format. Thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of thedisclosure. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges as well asindividual numerical values within that range (e.g. 1 to 5 includes 1,1.5, 2, 2.75, 3, 3.80, 4, and 5).

So that the present disclosure may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe disclosure pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present disclosure without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present disclosure, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through error in these procedures; throughdifferences in the manufacture, source, or purity of the ingredientsused to make the compositions or carry out the methods; and the like.The term “about” also encompasses amounts that differ due to novelequilibrium conditions for a composition resulting from a particularinitial mixture. Whether or not modified by the term “about”, the claimsinclude equivalents to the quantities.

As used herein, “substituted” refers to an organic group as definedbelow (e.g., an alkyl group) in which one or more bonds to a hydrogenatom contained therein are replaced by a bond to non-hydrogen ornon-carbon atoms. Substituted groups also include groups in which one ormore bonds to carbon(s) or hydrogen(s) atom replaced by one or morebonds, including double or triple bonds, to a heteroatom. Thus, asubstituted group is substituted with one or more substituents, unlessotherwise specified. A substituted group can be substituted with 1, 2,3, 4, 5, or 6 substituents.

Substituted ring groups include rings and ring systems in which a bondto a hydrogen atom is replaced with a bond to a carbon atom. Therefore,substituted cycloalkyl, aryl, heterocyclyl, and heteroaryl groups mayalso be substituted with substituted or unsubstituted alkyl, alkenyl,and alkynyl groups are defined herein.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

In some embodiments, substituted alkyls can include a heterocyclicgroup. As used herein, the term “heterocyclic group” includes closedring structures analogous to carbocyclic groups in which one or more ofthe carbon atoms in the ring is an element other than carbon, forexample, nitrogen, sulfur or oxygen. Heterocyclic groups may besaturated or unsaturated. Exemplary heterocyclic groups include, but arenot limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan.

Alkenyl groups or alkenes are straight chain, branched, or cyclic alkylgroups having two to about 30 carbon atoms, and further including atleast one double bond. In some embodiments, an alkenyl group has from 2to about carbon, or typically, from 2 to 10 carbon atoms. Alkenyl groupsmay be substituted or unsubstituted. For a double bond in an alkenylgroup, the configuration for the double bond can be a trans or cisconfiguration. Alkenyl groups may be substituted similarly to alkylgroups.

Alkynyl groups are straight chain, branched, or cyclic alkyl groupshaving two to about 30 carbon atoms, and further including at least onetriple bond. In some embodiments, an alkynyl group has from 2 to aboutcarbon, or typically, from 2 to 10 carbon atoms. Alkynyl groups may besubstituted or unsubstituted. Alkynyl groups may be substitutedsimilarly to alkyl or alkenyl groups.

As used herein, the terms “alkylene”, cycloalkylene”, alkynylides, andalkenylene”, alone or as part of another substituent, refer to adivalent radical derived from an alkyl, cycloalkyl, or alkenyl group,respectively, as exemplified by —CH₂CH₂CH₂—. For alkylene,cycloalkylene, alkynylene, and alkenylene groups, no orientation of thelinking group is implied.

The term “ester” as used herein refers to —R³⁰COOR³¹ group. R³⁰ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein. R³¹ is a substituted orunsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl,heterocyclylalkyl, or heterocyclyl group as defined herein.

The term “amine” (or “amino”) as used herein refers to —R³²NR³³R³⁴groups. R³² is absent, a substituted or unsubstituted alkylene,cycloalkylene, alkenylene, alkynylene, arylene, aralkylene,heterocyclylalkylene, or heterocyclylene group as defined herein. R³³and R³⁴ are independently hydrogen, or a substituted or unsubstitutedalkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl,or heterocyclyl group as defined herein.

The term “amine” as used herein also refers to an independent compound.When an amine is a compound, it can be represented by a formula ofR^(32′)NR^(33′)R^(34′) groups, wherein R^(32′), R^(33′), and R³⁴ areindependently hydrogen, or a substituted or unsubstituted alkyl,cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, orheterocyclyl group as defined herein.

The term “alcohol” as used herein refers to —R³⁵OH groups. R³⁵ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein.

The term “carboxylic acid” as used herein refers to —R³⁶COOH groups. R³⁶is absent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein.

The term “ether” as used herein refers to —R³⁷OR³⁸ groups. R³⁷ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein. R³⁸ is a substituted orunsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl,heterocyclylalkyl, or heterocyclyl group as defined herein.

The term “solvent” as used herein refers to any inorganic or organicsolvent. Solvents are useful in the disclosed method or article,product, or composition as reaction solvent or carrier solvent. Suitablesolvents include, but are not limited to, oxygenated solvents such aslower alkanols, lower alkyl ethers, glycols, aryl glycol ethers andlower alkyl glycol ethers. Examples of other solvents include, but arenot limited to, methanol, ethanol, propanol, isopropanol and butanol,isobutanol, ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, mixed ethylene-propylene glycolethers, ethylene glycol phenyl ether, and propylene glycol phenyl ether.Water is a solvent too. The solvent used herein can be of a singlesolvent or a mixture of many different solvents.

Glycol ethers include, but are not limited to, diethylene glycol n-butylether, diethylene glycol n-propyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, diethylene glycol t-butyl ether,dipropylene glycol n-butyl ether, dipropylene glycol methyl ether,dipropylene glycol ethyl ether, dipropylene glycol propyl ether,dipropylene glycol tert-butyl ether, ethylene glycol butyl ether,ethylene glycol propyl ether, ethylene glycol ethyl ether, ethyleneglycol methyl ether, ethylene glycol methyl ether acetate, propyleneglycol n-butyl ether, propylene glycol ethyl ether, propylene glycolmethyl ether, propylene glycol n-propyl ether, tripropylene glycolmethyl ether and tripropylene glycol n-butyl ether, ethylene glycolphenyl ether, propylene glycol phenyl ether, and the like, or mixturesthereof.

Di-Cationic or Di-Anionic Compounds Derived from an Aza-Michael AdditionReaction Between a Primary Amine and an Activated Olefin

The di-cationic or di-anionic compounds disclosed herein are derivedfrom an aza-Michael Addition Reaction between a primary amine (Michaeldonor) and an activated olefin (Michael acceptor) containing ahydrophilic ionic group at a temperature of from about −20° C. to about200° C., in some embodiments, for from about 10 minutes to about 48hours.

An aliphatic amine group may undergo an aza-Michael Addition reactionwhen in contact with an unsaturated hydrocarbon moiety (e.g.,carbon-carbon double bond) that is in proximity of an electronwithdrawing group such as carbonyl, cyano, or nitro group. Specifically,the Michael addition is a reaction between nucleophiles and activatedolefin and alkyne functionalities, wherein the nucleophile adds across acarbon-carbon multiple bond that is adjacent to an electron withdrawingand resonance stabilizing activating group, such as a carbonyl group.The Michael addition nucleophile is known as the “Michael donor”, theactivated electrophilic olefin is known as the “Michael acceptor”, andreaction product of the two components is known as the “Michael adduct.”Examples of Michael donors include, but are not restricted to, amines,thiols, phosphines, carbanions, and alkoxides. Examples of Michaelacceptors include, but are not restricted to, acrylate esters, alkylmethacrylates, acrylonitrile, acrylamides, maleimides, cyanoacrylatesand vinyl sulfones, vinyl ketones, nitro ethylenes, α, β-unsaturatedaldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridines, azocompounds, beta-keto acetylenes and acetylene esters.

As used herein, an “activated olefin” refers to a substituted alkene inwhich at least one of the double-bond carbon has a conjugated electronwithdrawing group. Examples of activated olefins include, but notlimited to, α, β-unsaturated carbonyl compounds (such asCH₂═CHCO—NH—CH₃, alkyl-CH═CH—CO-alkyl, CH₂═CH₂C(O)—O—CH₃), CH₂═CH—COOH,CH₂═CH(CH₃)—COOH, CH₂═CH—SO₃H, and like.

It was found that the Aza-Michael addition can be used to synthesize thedisclosed di-cationic or di-anionic compounds under mild conditions andwith a high yield for the compounds used in the disclosed methods orcompositions herein in a reasonable reaction time as descripted above.

Aza-Michael addition reaction can be catalyzed by a strong acid or base.In some cases, some ionic liquids can function both as reaction mediaand catalyst. The preferred catalyst for the Aza-Michael additionreaction to synthesize the disclosed compounds is a base. Exemplary basecatalyst can be hydroxide and amines. If the reaction to synthesize thedisclosed compounds includes a primary amine or a molecule having aprime amine group, the primary amine or the molecule itself can functionas a catalyst for the reaction. In such embodiments, no additionalcatalyst is necessary, or an additional catalyst is optional. Otherpreferred catalysts include amidine and guanidine bases.

The use of solvent and/or diluent for the reaction is optional. Whenemployed, a wide range of non-acidic solvents are suitable, such as, forexample, water, ethers (e.g., tetrahydrofuran (THF)), aromatichydrocarbons (e.g., toluene and xylene), alcohols (e.g., n-butanol),esters (e.g., ethyl 3-ethoxypropionate), and the like. A wide range ofsolvents can be used for the reaction because the synthesis process isrelatively insensitive to solvent. When solvent (or diluent) isemployed, loading levels can range from as low as about 10 wt-% up toabout 80 wt-% and higher. The solvent loading level can be about 0 wt-%,from about 1 wt-% to about 10 wt-%, from about 10 wt-% to about 20 wt-%,from about 20 wt-% to about 30 wt-%, from about 30 wt-% to about 40wt-%, from about 40 wt-% to about 50 wt-%, from about 50 wt-% to about60 wt-%, from about 60 wt-% to about 70 wt-%, from about 70 wt-% toabout 80 wt-%, from about 1 wt-% to about 20 wt-%, from about 20 wt-% toabout 40 wt-%, from about 40 wt-% to about 60 wt-%, from about 60 wt-%to about 80 wt-%, from about 40 wt-% to about 70 wt-%, about 5 wt-%,about 15 wt-%, about 25 wt-%, about 35 wt-%, about 45 wt-%, about 55wt-%, about 65 wt-%, about 75 wt-%, or any value there between of thefinal reaction mixture.

Generally, the reaction can be carried out at a temperature over a widerange of temperatures. The reaction temperature can range from about−20° C. to about 200° C., from about 0° C. to about 150° C., morepreferably from about 50° C. to about 80° C. The contacting temperaturecan be from about 10° C. to about 140° C., about 20° C. to about 130°C., about 30° C. to about 120° C., about 40° C. to about 110° C., about50° C. to about 100° C., about 60° C. to about 90° C., about 70° C. toabout 80° C., about 0° C. to about 20° C., about 20° C. to about 40° C.,about 40° C. to about 60° C., about 60° C. to about 80° C., about 80° C.to about 100° C., about 100° C. to about 120° C., about 120° C. to about150° C., about 5° C., about 25° C., about 45° C., about 65° C., about85° C., about 105° C., about 125° C., about 145° C., or any value therebetween. The reaction temperature can be about the same from starting ofthe reaction to end of the reaction and can be changed from onetemperature to another while the reaction is going on.

The reaction time for the synthesis of the compounds disclosed hereincan vary widely, depending on such factors as the reaction temperature,the efficacy and amount of the catalyst, the presence or absence ofdiluent (solvent), and the like. The preferred reaction time can be fromabout 10 minutes to about 48 hours, from about 0.5 hours to about 48hours, from about 1 hour to 40 hours, from about 2 hours to 38 hours,from about 4 hours to about 36 hours, from 6 hours to about 34 hours,from about 8 hours to about 32 hours, from about 10 hours to about 30hours, from about 12 hours to about 28 hours, from about 14 hours to 26hours, from about 16 hours to 24 hours, from about 18 hours to 20 hours,from about 1 hour to 8 hours, from 8 hours to 16 hours, from 8 hours toabout 24 hours, about 2 hours, about 4 hours, about 6 hours, about 8hours, about 10 hours, about 14 hours, about 16 hours, about 18 hours,about 24 hours, about 30 hours, about 36 hours, or any values therebetween.

The reaction for the synthesis of the compounds disclosed herein can goto completion when one mole of the primary amine or polyamine and two ormore moles of the activated olefin, are mixed together for a sufficientof time at a temperature described above.

The progression of the reaction can be typically monitored by ESI-MSand/or NMR spectroscopy for consumption of the monomer. The reactionproducts can be purified or separated by HPLC or other methods known byone skilled in the art. For reactions that proceeded to completion, theformed product was separated by removal of solvent or by precipitationin a non-polar solvent that was the opposite of the reaction media. Forthe reactions in water, the formed product was precipitated from theaqueous reaction mixture. Higher pressure can speed-up the reaction.Typically, if the reaction is carried out at a room temperature, thereaction can have a product yield of more than 98% in 16 hours.

Additional Corrosion Control Composition Agent in a Corrosion ControlComposition

In addition to one or more di-cationic di-anionic compounds derived fromprimary amines as described herein, a corrosion control composition inthe present disclosure comprises one or more additional corrosioncontrol composition agents.

The additional corrosion control composition agent in the disclosedcorrosion control compositions can include, but is not limited to, acarrier, acid, dispersant, biocide, additional corrosion inhibitor,fouling control agent, antioxidant, polymer degradation preventionagent, permeability modifier, foaming agent, antifoaming agent,fracturing proppant, scavenger for H₂S, CO₂, and/or O₂, gelling agent,lubricant, and friction reducing agent, salt, or mixture thereof.

The additional corrosion control composition agent in the disclosedcorrosion control compositions can also include, but not be limited to,an organic sulfur compound, asphaltene inhibitor, paraffin inhibitor,scale inhibitor, water clarifier, emulsion breaker, reverse emulsionbreaker, gas hydrate inhibitor, a pH modifier, a surfactant, or acombination thereof.

Furthermore, the additional corrosion control composition agent can be asequestrant, solubilizer, lubricant, buffer, cleaning agent, rinse aid,preservative, binder, thickener or other viscosity modifier, processingaid, carrier, water-conditioning agent, or foam generator, thresholdagent or system, aesthetic enhancing agent (e.g., dye, odorant,perfume), or other additive suitable for formulation with a reverseemulsion breaker, or mixtures thereof.

The additional corrosion control composition agent in a corrosioncontrol composition disclosed herein will vary according to the specificcorrosion control composition being manufactured and its intend use asone skilled in the art will appreciate.

Alternatively, the corrosion control composition does not contain or isfree of one or more of the additional corrosion control compositionagents.

When one or more additional corrosion control composition agents areused in the corrosion control compositions disclosed herein, they can beformulated together with the di-cationic or di-anionic compounds asdescribed here in the same corrosion control compositions.Alternatively, some or all the additional corrosion control compositionagents can be formulated into one or more different formulations and besupplied to the water systems or surfaces. In other words, theadditional corrosion control composition agents can be provided into awater system or onto a surface independently, simultaneously, orsequentially.

Biocide and Carrier

In some embodiments, the corrosion control compositions disclosed hereinfurther include a biocide, in addition to the di-cationic or di-anioniccompounds. In some other embodiments, the disclosed corrosion controlcompositions herein further include a carrier. In some otherembodiments, the disclosed corrosion control compositions herein furtherinclude a biocide and carrier. In some embodiments, the disclosedmethods or corrosion control compositions herein may consist of one ormore di-cationic or di-anionic compounds disclosed herein and carrier.In some embodiments, the corrosion control compositions disclosed hereinconsist of one or more di-cationic or di-anionic compounds disclosedherein, a carrier, and a biocide.

Biocides suitable for use may be oxidizing or non-oxidizing biocides.Oxidizing biocides include, but are not limited to, bleach, chlorine,bromine, chlorine dioxide, and materials capable of releasing chlorineand bromine. Non-oxidizing biocides include, but are not limited to,glutaraldehyde, isothiazolin, 2,2-dibromo-3-nitrilopropionamide,2-bromo-2-nitropropane-1,3 diol,1-bromo-1-(bromomethyl)-1,3-propanedicarbonitrile,tetrachloroisophthalonitrile, alkyldimethylbenzylammonium chloride,dimethyl dialkyl ammonium chloride, didecyl dimethyl ammonium chloride,poly(oxyethylene(dimethyliminio)ethylene(dimethyliminio)ethylenedichloride, methylene bisthiocyanate, 2-decylthioethanamine,tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate,cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-1-ethanol,2-(2-bromo-2-nitroethenyl)furan, beta-bromo-beta-nitrostyrene,beta-nitrostyrene, beta-nitrovinyl furan, 2-bromo-2-bromomethylglutaronitrile, bis(trichloromethyl) sulfone,S-(2-hydroxypropyl)thiomethanesulfonate,tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione,2-(thiocyanomethylthio)benzothiazole, 2-bromo-4′-hydroxyacetophenone,1,4-bis(bromoacetoxy)-2-butene, bis(tributyltin)oxide,2-(tert-butylamino)-4-chloro-6-(ethylamino)-s-triazine, dodecylguanidineacetate, dodecylguanidine hydrochloride, coco alkyldimethylamine oxide,n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride,7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid,4,5-dichloro-2-n-octyl-4-isothiazoline-3-one,5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one.

Suitable non-oxidizing biocides also include, for example, aldehydes(e.g., formaldehyde, glutaraldehyde, and acrolein), amine-type compounds(e.g., quaternary amine compounds and cocodiamine), halogenatedcompounds (e.g., 2-bromo-2-nitropropane-3-diol (Bronopol) and2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (e.g.,isothiazolone, carbamates, and metronidazole), and quaternaryphosphonium salts (e.g., tetrakis(hydroxymethyl)-phosphonium sulfate(THPS)).

Suitable oxidizing biocides include, for example, sodium hypochlorite,trichloroisocyanuric acids, dichloroisocyanuric acid, calciumhypochlorite, lithium hypochlorite, chlorinated hydantoins, stabilizedsodium hypobromite, activated sodium bromide, brominated hydantoins,chlorine dioxide, ozone, peroxycarboxylic acid, peroxycarboxylic acidcomposition, and peroxides.

The corrosion control composition can comprise from about 0.1 wt-% toabout 10 wt-%, from about 0.5 wt-% to about 5 wt-%, or from about 0.5wt-% to about 4 wt-% of a biocide, based on total weight of thecomposition. In some embodiments, the corrosion control composition isfree of a biocide. In some embodiments, the corrosion controlcomposition is free of an oxidizing biocide. In some other embodiments,the corrosion control composition is free of a non-oxidizing biocide.

A carrier in the disclosed corrosion control composition can be water,an organic solvent, or a combination of water and an organic solvent.The organic solvent can be an alcohol, a hydrocarbon, a ketone, anether, an alkylene glycol, a glycol ether, an amide, a nitrile, asulfoxide, an ester, or a combination thereof. Examples of suitableorganic solvents include, but are not limited to, methanol, ethanol,propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol,decanol, 2-butoxyethanol, methylene glycol, ethylene glycol,1,2-propylene glycol, 1,3-propylene glycol, diethyleneglycol monomethylether, diethylene glycol monoethyl ether, ethylene glycol monobutylether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane,methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene,heavy aromatic naphtha, cyclohexanone, diisobutylketone, diethyl ether,propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, or acombination thereof.

The corrosion control composition can comprise from about 1 wt-% toabout 80 wt-%, from about 1 wt-% to about 70 wt-%, from about 1 wt-% toabout 60 wt-%, from about 1 wt-% to about 50 wt-%, from about 1 wt-% toabout 40 wt-%, from about 1 wt-% to about 30 wt-%, from about 1 wt-% toabout 20 wt-%, from about 1 wt-% to about 10 wt-%, from about 5 wt-% toabout 10 wt-%, from about 5 wt-% to about 20 wt-%, from about 5 wt-% toabout 30 wt-%, from about 5 wt-% to about 40 wt-%, from about 5 wt-% toabout 50 wt-%, from about 10 wt-% to about 20 wt-%, from about 10 wt-%to about 30 wt-%, from about 10 to about 40 wt-%, from about 10 wt-% toabout 50 wt-%, about 10 wt-%, about 20 wt-%, about 30 wt-%, about 40-%,about 50 wt-%, about 60 wt-%, about 70 wt-%, about 80 wt-%, about 90wt-%, or any value there between of the one or more carrier, based ontotal weight of the composition.

Acids

Generally, acids, as used in this disclosure, include both organic andinorganic acids. Organic acids include, but not limited to,hydroxyacetic (glycolic) acid, formic acid, acetic acid, propionic acid,butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid,trichloroacetic acid, urea hydrochloride, and benzoic acid. Organicacids also include dicarboxylic acids such as oxalic acid, malonic acid,succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid,and terephthalic acid. Combinations of these organic acids can also beused. Inorganic acids include, but are not limited to, mineral acids,such as phosphoric acid, sulfuric acid, sulfamic acid, methylsulfamicacid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, and nitricacid. Inorganic acids can be used alone, in combination with otherinorganic acid(s), or in combination with one or more organic acid. Acidgenerators can be used to form a suitable acid, including for examplegenerators such as potassium fluoride, sodium fluoride, lithiumfluoride, ammonium fluoride, ammonium bifluoride, sodium silicofluoride,etc.

Examples of particularly suitable acids in this the methods orcompositions disclosed herein include inorganic and organic acids.Exemplary inorganic acids include phosphoric, phosphonic, sulfuric,sulfamic, methylsulfamic, hydrochloric, hydrobromic, hydrofluoric, andnitric. Exemplary organic acids include hydroxyacetic (glycolic),citric, lactic, formic, acetic, propionic, butyric, valeric, caproic,gluconic, itaconic, trichloroacetic, urea hydrochloride, and benzoic.Organic dicarboxylic acids can also be used such as oxalic, maleic,fumaric, adipic, and terephthalic acid.

Percarboxylic Acids and Peroxycarboxylic Acid Compositions

A peroxycarboxylic acid (i.e. peracid) or peroxycarboxylic acidcomposition can be included in the articles, products, or compositionsdisclosed herein. As used herein, the term “peracid” may also bereferred to as a “percarboxylic acid,” “peroxycarboxylic acid” or“peroxyacid.” Sulfoperoxycarboxylic acids, sulfonated peracids andsulfonated peroxycarboxylic acids are also included within the terms“peroxycarboxylic acid” and “peracid” as used herein. As one of skill inthe art appreciates, a peracid refers to an acid having the hydrogen ofthe hydroxyl group in carboxylic acid replaced by a hydroxy group.Oxidizing peracids may also be referred to herein as peroxycarboxylicacids.

A peracid includes any compound of the formula R—(COOOH)_(n) in which Rcan be hydrogen, alkyl, alkenyl, alkyne, acrylic, alicyclic group, aryl,heteroaryl, or heterocyclic group, and n is 1, 2, or 3, and named byprefixing the parent acid with peroxy. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acrylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined herein.

A peroxycarboxylic acid composition, as used herein, refers to anycomposition that comprises one or more peracids, their correspondingacids, and hydrogen peroxide or or other oxidizing agents. Aperoxycarboxylic acid composition can also include a stabilizer,fluorescent active tracer or compound, or other ingredients, as oneskilled in the other would know.

As used herein, the terms “mixed” or “mixture” when used relating to“percarboxylic acid composition,” “percarboxylic acids,”“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one percarboxylic acid orperoxycarboxylic acid. Peracids such as peroxyacetic acid andperoxyoctanoic acid may also be used. Any combination of these acids mayalso be used.

Alkalinity Source

The disclosed corrosion control compositions or methods of using thereofmay include using an effective amount of an alkalinity source. Thealkalinity source in turn comprises one or more alkaline compounds.

In general, an effective amount of the alkalinity source should beconsidered as an amount that provides a reaction mixture having a pH ofat least about 8. When the solution has a pH of between about 8 andabout 10, it can be considered mildly alkaline, and when the pH isgreater than about 12, the solution can be considered caustic.

The alkalinity source can include an alkali metal carbonate, an alkalimetal hydroxide, alkaline metal silicate, alkaline metal metasilicate,or a mixture thereof. Suitable metal carbonates that can be usedinclude, for example, sodium or potassium carbonate, bicarbonate,sesquicarbonate, or a mixture thereof. Suitable alkali metal hydroxidesthat can be used include, for example, sodium, lithium, or potassiumhydroxide. Examples of useful alkaline metal silicates include sodium orpotassium silicate (with M₂O:SiO₂ ratio of 2.4 to 5:1, M representing analkali metal) or metasilicate. A metasilicate can be made by mixing ahydroxide and silicate. The alkalinity source may also include a metalborate such as sodium or potassium borate, and the like.

The alkalinity source may also include ethanolamines, urea sulfate,amines, amine salts, and quaternary ammonium. The simplest cationicamines, amine salts and quaternary ammonium compounds can beschematically drawn thus:

in which, R represents a long alkyl chain, R′, R″, and R′″ may be eitherlong alkyl chains or smaller alkyl or aryl groups or hydrogen and Xrepresents an anion.

In some embodiments, the alkalinity source is dimethylethanolamine,methoxypropylamine, monoethanolamine, or mixture thereof.

Additional Corrosion Inhibitor

In some embodiments, the corrosion control compositions disclosed hereinfurther include an additional corrosion inhibitor. In some otherembodiments, the disclosed corrosion control compositions herein furtherinclude an additional corrosion inhibitor and carrier. In some otherembodiments, the disclosed corrosion control compositions herein furtherinclude an additional corrosion inhibitor, biocide, and carrier. In someembodiments, the disclosed control compositions herein may consist ofone or more di-cationic or di-anionic compounds disclosed herein, one ormore additional corrosion inhibitors, and carrier. In some embodiments,the corrosion control compositions disclosed herein consist of one ormore di-cationic or di-anionic compounds disclosed herein, a carrier,additional corrosion inhibitor, and biocide.

The corrosion control composition can comprise from about 0.1 wt-% toabout 20 wt-%, from about 0.1 wt-% to about 10 wt-%, or from 0.1 toabout 5 wt-% of the one or more additional corrosion inhibitors, basedon total weight of the composition. A composition of the disclosure cancomprise from 0 wt-% to 10 percent by weight of the one or moreadditional corrosion inhibitors, based on total weight of thecomposition. The composition can comprise about 1.0 wt-%, about 1.5wt-%, about 2.0 wt-%, about 2.5 wt-%, about 3.0 wt-%, about 3.5 wt-%,about 4.0 wt-%, about 4.5 wt-%, about 5.0 wt-%, about 5.5 wt-%, about6.0 wt-%, about 6.5 wt-%, about 7.0 wt-%, about 7.5 wt-%, about 8.0wt-%, about 8.5 wt-%, about 9.0 wt-%, about 9.5 wt-%, about 10.0 wt-%,about 10.5 wt-%, about 11.0 wt-%, about 11.5 wt-%, about 12.0 wt-%,about 12.5 wt-%, about 13.0 wt-%, about 13.5 wt-%, about 14.0 wt-%,about 14.5 wt-%, or about 15.0 wt-% of or any value or range therebetween of the one or more additional corrosion inhibitors, based ontotal weight of the composition. A specific water system can have itsown requirements for using one or more additional corrosion inhibitors,and the weight percent of one or more additional corrosion inhibitors inthe composition can vary with the water system in which it is used.

Additional corrosion inhibitors for multi-metal protection are typicallytriazoles, such as, but not limited to, benzotriazole, halogenatedtriazoles, and nitro-substituted azoles.

The one or more additional corrosion inhibitors can be an imidazolinecompound, a quaternary ammonium compound, a pyridinium compound, or acombination thereof.

The one or more additional corrosion inhibitors can be an imidazoline.The imidazoline can be, for example, imidazoline derived from a diamine,such as ethylene diamine (EDA), diethylene triamine (DETA), triethylenetetraamine (TETA) etc. and a long chain fatty acid such as tall oilfatty acid (TOFA). The imidazoline can be an imidazoline of Formula (1A)or an imidazoline derivative. Representative imidazoline derivativesinclude an imidazolinium compound of Formula (2A) or a bis-quaternizedcompound of Formula (3A).

The one or more additional corrosion inhibitors can include animidazoline of Formula (1A):

wherein R^(10a) is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R^(11a)is hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆ arylalkyl; andR^(12a) and R^(13a) are independently hydrogen or a C₁-C₆ alkyl group.Preferably, the imidazoline includes an R^(10a) which is the alkylmixture typical in tall oil fatty acid (TOFA), and R^(11a), R^(12a) andR^(13a) are each hydrogen.

The one or more additional corrosion inhibitors can be an imidazoliniumcompound of Formula (2A):

wherein R^(10a) is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R^(11a)and R^(14a) are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,or C₁-C₆ arylalkyl; R^(12a) and R^(13a) are independently hydrogen or aC₁-C₆ alkyl group; and X⁻ is a halide (such as chloride, bromide, oriodide), carbonate, sulfonate, phosphate, or the anion of an organiccarboxylic acid (such as acetate). Preferably, the imidazoliniumcompound includes 1-benzyl-1-(2-hydroxyethyl)-2-tall-oil-2-imidazoliniumchloride.

The one or more additional corrosion inhibitors can be a bis-quaternizedcompound having the formula (3A):

wherein R^(1a) and R^(2a) are each independently unsubstituted branched,chain or ring alkyl or alkenyl having from 1 to about 29 carbon atoms;partially or fully oxygenized, sulfurized, and/or phosphorylizedbranched, chain, or ring alkyl or alkenyl having from 1 to about 29carbon atoms; or a combination thereof; R^(3a) and R^(4a) are eachindependently unsubstituted branched, chain or ring alkylene oralkenylene having from 1 to about 29 carbon atoms; partially or fullyoxygenized, sulfurized, and/or phosphorylized branched, chain, or ringalkylene or alkenylene having from 1 to about 29 carbon atoms; or acombination thereof; L₁ and L₂ are each independently absent, H, —COOH,—SO₃H, —PO₃H, —COOR^(5a), —CONH₂, —CONHR^(5a), or —CON(R^(5a))₂; R^(5a)is each independently a branched or unbranched alkyl, aryl, alkylaryl,alkylheteroaryl, cycloalkyl, or heteroaryl group having from 1 to about10 carbon atoms; n is 0 or 1, and when n is 0, L₂ is absent or H; x isfrom 1 to about 10; and y is from 1 to about 5. Preferably, R^(1a) andR^(2a) are each independently C₆-C₂₂ alkyl, C₅-C₂₀ alkyl, C₁₂-C₁₈ alkyl,C₁₆-C₁₈ alkyl, or a combination thereof; R^(3a) and R^(4a) are C₁-C₁₀alkylene, C₂-C₈ alkylene, C₂-C₆ alkylene, or C₂-C₃ alkylene; n is 0 or1; x is 2; y is 1; R³ and R⁴ are —C₂H₂—; L₁ is —COOH, —SO₃H, or —PO₃H;and L₂ is absent, H, —COOH, —SO₃H, or —PO₃H. For example, R^(1a) andR^(2a) can be derived from a mixture of tall oil fatty acids and arepredominantly a mixture of C₁₇H₃₃ and C₁₇H₃₁ or can be C₁₆-C₁₈ alkyl;R^(3a) and R^(4a) can be C₂-C₃ alkylene such as —C₂H₂—; n is 1 and L₂ is—COOH or n is 0 and L₂ is absent or H; x is 2; y is 1; R^(3a) and R^(4a)are —C₂H₂—; and L₁ is —COOH.

It should be appreciated that the number of carbon atoms specified foreach group of formula (3A) refers to the main chain of carbon atoms anddoes not include carbon atoms that may be contributed by substituents.

The one or more additional corrosion inhibitors can be a bis-quaternizedimidazoline compound having the formula (3A) wherein R^(1a) and R^(2a)are each independently C₆-C₂₂ alkyl, C₈-C₂₀ alkyl, C₁₂-C₁₈ alkyl, orC₁₆-C₁₈ alkyl or a combination thereof; R^(4a) is C₁-C₁₀ alkylene, C₂-C₈alkylene, C₂-C₆ alkylene, or C₂-C₃ alkylene; x is 2; y is 1; n is 0; L₁is —COOH, —SO₃H, or —PO₃H; and L₂ is absent or H. Preferably, abis-quaternized compound has the formula (3A) wherein R^(1a) and R^(2a)are each independently C₁₆-C₁₈ alkyl; R^(4a) is —C₂H₂—; x is 2; y is 1;n is 0; L₁ is —COOH, —SO₃H, or —PO₃H and L₂ is absent or H.

The one or more additional corrosion inhibitors can be a quaternaryammonium compound of Formula (4A):

wherein R^(1a), R^(2a), and R^(3a) are independently C₁ to C₂₀ alkyl,R^(4a) is methyl or benzyl, and X⁻ is a halide or methosulfate.

Suitable alkyl, hydroxyalkyl, alkylaryl, arylalkyl or aryl aminequaternary salts include those alkylaryl, arylalkyl and aryl aminequaternary salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻] whereinR^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbon atoms, and Xis Cl, Br or I. For the quaternary salts, R^(5a), R^(6a), R^(7a), andR^(8a) can each be independently alkyl (e.g., C₁-C₁₈ alkyl),hydroxyalkyl (e.g., C₁-C₁₈ hydroxyalkyl), and arylalkyl (e.g., benzyl).The mono or polycyclic aromatic amine salt with an alkyl or alkylarylhalide include salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻]wherein R^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbonatoms and at least one aryl group, and X is Cl, Br or I.

Suitable quaternary ammonium salts include, but are not limited to, atetramethyl ammonium salt, a tetraethyl ammonium salt, a tetrapropylammonium salt, a tetrabutyl ammonium salt, a tetrahexyl ammonium salt, atetraoctyl ammonium salt, a benzyltrimethyl ammonium salt, abenzyltriethyl ammonium salt, a phenyltrimethyl ammonium salt, aphenyltriethyl ammonium salt, a cetyl benzyldimethyl ammonium salt, ahexadecyl trimethyl ammonium salt, a dimethyl alkyl benzyl quaternaryammonium salt, a monomethyl dialkyl benzyl quaternary ammonium salt, ora trialkyl benzyl quaternary ammonium salt, wherein the alkyl group hasabout 6 to about 24 carbon atoms, about 10 and about 18 carbon atoms, orabout 12 to about 16 carbon atoms. The quaternary ammonium salt can be abenzyl trialkyl quaternary ammonium salt, a benzyl triethanolaminequaternary ammonium salt, or a benzyl dimethylaminoethanolaminequaternary ammonium salt.

The one or more additional corrosion inhibitors can be a pyridinium saltsuch as those represented by Formula (5A):

wherein R^(9a) is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atoms and X⁻ isa halide such as chloride, bromide, or iodide. Among these compounds arealkyl pyridinium salts and alkyl pyridinium benzyl quats. Exemplarycompounds include methyl pyridinium chloride, ethyl pyridinium chloride,propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridiniumchloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetylpyridinium chloride, benzyl pyridinium chloride and an alkyl benzylpyridinium chloride, preferably wherein the alkyl is a C₁-C₆ hydrocarbylgroup. Preferably, the pyridinium compound includes benzyl pyridiniumchloride.

The one or more additional corrosion inhibitors can be a phosphateester, monomeric or oligomeric fatty acid, alkoxylated amine, or mixturethereof.

The one or more additional corrosion inhibitors can be a phosphateester. Suitable mono-, di- and tri-alkyl as well as alkylaryl phosphateesters and phosphate esters of mono, di, and triethanolamine typicallycontain between from 1 to about 18 carbon atoms. Preferred mono-, di-and trialkyl phosphate esters, alkylaryl or arylalkyl phosphate estersare those prepared by reacting a C₃-C₁₈ aliphatic alcohol withphosphorous pentoxide. The phosphate intermediate interchanges its estergroups with triethylphosphate producing a broader distribution of alkylphosphate esters.

Alternatively, the phosphate ester can be made by admixing with an alkyldiester, a mixture of low molecular weight alkyl alcohols or diols. Thelow molecular weight alkyl alcohols or diols preferably include C₆ toC₁₀ alcohols or diols. Further, phosphate esters of polyols and theirsalts containing one or more 2-hydroxyethyl groups, and hydroxylaminephosphate esters obtained by reacting polyphosphoric acid or phosphoruspentoxide with hydroxylamines such as diethanolamine or triethanolamineare preferred.

The one or more additional corrosion inhibitors can be a monomeric oroligomeric fatty acid. Preferred monomeric or oligomeric fatty acids areC₁₄-C₂₂ saturated and unsaturated fatty acids as well as dimer, trimerand oligomer products obtained by polymerizing one or more of such fattyacids.

The one or more additional corrosion inhibitors can be an alkoxylatedamine. The alkoxylated amine can be an ethoxylated alkyl amine. Thealkoxylated amine can be ethoxylated tallow amine.

In some embodiments, the additional corrosion inhibitor in the corrosioncontrol composition is tall oil diethylenetriamine imidazoline,1-(2-hydroxyethyl)-2-coconut oil-2-imidazoline,1-benzyl-1-(2-hydroxyethyl)-2-coconut oil-2-imidazolinium chloride,benzyl-dimethyl-dodecyl-ammonium chloride, N-coco alkyl 1,3,propylenediamine acetate, morpholine, morpholine derivative,didecyl-dimethyl-ammonium chloride, 1-benzyl-1-(2-hydroxyethyl)-2-talloil-2-imidazolinium chloride, and N-benzyl-alkylpyridinium chloride.tall oil fatty acid, trimeric C18 unsaturated fatty acid, dimeric C18unsaturated fatty acid, alkylpyridine, N-benzyl-alkylpyridiniumchloride, quinoline, quinoline quaternary compound with benzyl chloride,or mixture thereof.

Dispersant

In some embodiments, the corrosion control compositions disclosed hereincan further comprise a dispersant. A dispersant keeps particulate matterpresent in the water of a water system dispersed, so that it does notagglomerate. The composition can comprise from about 0.1 to 10 wt-%,from about 0.5 to 5 wt-%, or from about 0.5 to 4 wt-% of a dispersant,based on total weight of the composition.

A dispersant may be an acrylic acid polymer, maleic acid polymer,copolymer of acrylic acid with sulfonated monomers, alkyl estersthereof, or combination thereof. These polymers may include terpolymersof acrylic acid, acrylamide and sulfonated monomers. These polymers mayalso include quad-polymers consisting of acrylic acid and three othermonomers.

Suitable dispersants include, but are not limited to, aliphaticphosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonicacid, and aminoalkyl phosphonic acids, e.g. polyaminomethylenephosphonates with 2-10 N atoms e.g. each bearing at least one methylenephosphonic acid group; examples of the latter are ethylenediaminetetra(methylene phosphonate), diethylenetriamine penta(methylenephosphonate), and the triamine- and tetramine-polymethylene phosphonateswith 2-4 methylene groups between each N atom, at least 2 of the numbersof methylene groups in each phosphonate being different. Other suitabledispersion agents include lignin, or derivatives of lignin such aslignosulfonate and naphthalene sulfonic acid and derivatives.

In some embodiments, the dispersant in the corrosion controlcompositions disclosed herein is a reaction product of tall oil fattyacids with diethylenetriamine and acrylic acid (1:1:1), reaction productof fatty acids or tall-oil with triethylenetetramine ortetraethylenepentamine, reaction product of diethylenetriamine andnapthenic acid.

The corrosion control composition can further comprise an organic sulfurcompound, such as a mercaptoalkyl alcohol, mercaptoacetic acid,thioglycolic acid, 3,3′-dithiodipropionic acid, sodium thiosulfate,thiourea, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammoniumthiosulfate, sodium thiocyanate, ammonium thiocyanate, sodiummetabisulfite, or a combination thereof. Preferably, the mercaptoalkylalcohol comprises 2-mercaptoethanol. Such compounds are used assynergists in the composition.

In some embodiments, the organic sulfur compound in the corrosioncontrol composition is 2 Mercaptoethanol, sodium thiosulfate,thioglycolic acid, or a mixture thereof.

The organic sulfur compound can constitute from about 0.5 wt-% to about15 wt-% of the composition, based on total weight of the composition,preferably from about 1 wt-% to about 10 wt-% and more preferably fromabout 1 wt-% to about 5 wt-%. The organic sulfur compound can constituteabout 1 wt-%, about 2 wt-%, about 3 wt-%, about 4 wt-%, about 5 wt-%,about 6 wt-%, about 7 wt-%, about 8 wt-%, about 9 wt-%, about 10 wt-%,about 11 wt-%, about 12 wt-%, about 13 wt-%, about 14 wt-%, or about 15wt-% of the composition.

The corrosion control composition can further comprise a de-emulsifier.Preferably, the demulsifier comprises an oxyalkylate polymer, such as apolyalkylene glycol. The de-emulsifier can constitute from about 0.1wt-% to about 10 wt-%, from about 0.5 wt-% to about 5 wt. %, or fromabout 0.5 wt-% to about 4 wt-% of the composition, based on total weightof the composition. The de-emulsifier can constitute about 0.5 wt-%,about 1 wt-%, about 1.5 wt-%, about 2 wt-%, about 2.5 wt-%, about 3wt-%, about 3.5 wt-%, about 4 wt-%, about 4.5 wt-%, or about 5 wt-% ofthe composition.

The corrosion control composition can further comprise an asphalteneinhibitor. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.1 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of an asphaltene inhibitor, based on total weight of thecomposition. Suitable asphaltene inhibitors include, but are not limitedto, aliphatic sulfonic acids; alkyl aryl sulfonic acids; arylsulfonates; lignosulfonates; alkylphenol/aldehyde resins and similarsulfonated resins; polyolefin esters; polyolefin imides; polyolefinesters with alkyl, alkylenephenyl or alkylenepyridyl functional groups;polyolefin amides; polyolefin amides with alkyl, alkylenephenyl oralkylenepyridyl functional groups; polyolefin imides with alkyl,alkylenephenyl or alkylenepyridyl functional groups; alkenyl/vinylpyrrolidone copolymers; graft polymers of polyolefins with maleicanhydride or vinyl imidazole; hyperbranched polyester amides;polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkylsuccinates, sorbitan monooleate, and polyisobutylene succinic anhydride.

The corrosion control composition can further comprise a paraffininhibitor. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.1 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of a paraffin inhibitor, based on total weight of thecomposition. Suitable paraffin inhibitors include, but are not limitedto, paraffin crystal modifiers, and dispersant/crystal modifiercombinations. Suitable paraffin crystal modifiers include, but are notlimited to, alkyl acrylate copolymers, alkyl acrylate vinylpyridinecopolymers, ethylene vinyl acetate copolymers, maleic anhydride estercopolymers, branched polyethylenes, naphthalene, anthracene,microcrystalline wax and/or asphaltenes. Suitable paraffin dispersantsinclude, but are not limited to, dodecyl benzene sulfonate, oxyalkylatedalkylphenols, and oxyalkylated alkylphenolic resins.

The corrosion control composition can further comprise a scaleinhibitor. The composition can comprise from about 0.1 wt-% to about 20wt-%, from about 0.5 wt-% to about 10 wt-%, or from about 1 wt-% toabout 10 wt-% of a scale inhibitor, based on total weight of thecomposition. Suitable scale inhibitors include, but are not limited to,phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonicacids, polyacrylamides, salts of acrylamidomethyl propanesulfonate/acrylic acid copolymer (AMPS/AA), phosphinated maleiccopolymer (PHOS/MA), mono-, bis- and oligomeric phosphinosuccinic acid(PSO) derivatives, polycarboxylic acid, hydrophobically modifiedpolycarboxylic acid, and salts of a polymaleic acid/acrylicacid/acrylamidomethyl propane sulfonate terpolymer (PMA/AA/AMPS).

The corrosion control composition can further comprise an emulsifier.The composition can comprise from about 0.1 wt-% to about 10 wt-%, fromabout 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% to about 4 wt-%of an emulsifier, based on total weight of the composition. Suitableemulsifiers include, but are not limited to, salts of carboxylic acids,products of acylation reactions between carboxylic acids or carboxylicanhydrides and amines, and alkyl, acyl and amide derivatives ofsaccharides (alkyl-saccharide emulsifiers).

The corrosion control composition can further comprise a waterclarifier. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of a water clarifier, based on total weight of thecomposition. Suitable water clarifiers include, but are not limited to,inorganic metal salts such as alum, aluminum chloride, and aluminumchlorohydrate, or organic polymers such as acrylic acid-based polymers,acrylamide-based polymers, polymerized amines, alkanolamines,thiocarbamates, and cationic polymers such as diallyldimethylammoniumchloride (DADMAC).

The corrosion control composition can further comprise an emulsionbreaker. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of an emulsion breaker, based on total weight of thecomposition. Suitable emulsion breakers include, but are not limited to,dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonicacid (NAXSA), epoxylated and propoxylated compounds, and resins, such asphenolic and epoxide resins.

The corrosion control composition can further comprise a hydrogensulfide scavenger. The composition can comprise from about 1 wt-% toabout 50 wt-%, from about 1 wt-% to about 40 wt-%, from about 1 wt-% toabout 30 wt-%, from about 0.1 wt-% to about 10 wt-%, from about 0.5 wt-%to about 5 wt-%, or from about 0.5 wt-% to about 4 wt-% of a hydrogensulfide scavenger, based on total weight of the composition. Suitableadditional hydrogen sulfide scavengers include, but are not limited to,oxidants (e.g., inorganic peroxides such as sodium peroxide or chlorinedioxide); aldehydes (e.g., of 1-10 carbons such as formaldehyde,glyoxal, glutaraldehyde, acrolein, or methacrolein; triazines (e.g.,monoethanolamine triazine, monomethylamine triazine, and triazines frommultiple amines or mixtures thereof); condensation products of secondaryor tertiary amines and aldehydes, and condensation products of alkylalcohols and aldehydes.

The corrosion control composition can further comprise a gas hydrateinhibitor. The composition can comprise from about 0.1 wt-% to about 25wt-%, from about 0.5 wt-% to about 20 wt-%, from about 1 wt-% to about10 wt-%, from about 0.1 wt-% to about 10 wt-%, from about 0.5 wt-% toabout 5 wt-%, or from about 0.5 wt-% to about 4 wt-% of a gas hydrateinhibitor, based on total weight of the composition. Suitable gashydrate inhibitors include, but are not limited to, thermodynamichydrate inhibitors (THI), kinetic hydrate inhibitors (KHI), andanti-agglomerates (AA). Suitable thermodynamic hydrate inhibitorsinclude, but are not limited to, sodium chloride, potassium chloride,calcium chloride, magnesium chloride, sodium bromide, formate brines(e.g. potassium formate), polyols (such as glucose, sucrose, fructose,maltose, lactose, gluconate, monoethylene glycol, diethylene glycol,triethylene glycol, mono-propylene glycol, dipropylene glycol,tripropylene glycols, tetrapropylene glycol, monobutylene glycol,dibutylene glycol, tributylene glycol, glycerol, diglycerol,triglycerol, and sugar alcohols (e.g. sorbitol, mannitol)), methanol,propanol, ethanol, glycol ethers (such as diethyleneglycolmonomethylether, ethyleneglycol monobutylether), and alkyl or cyclicesters of alcohols (such as ethyl lactate, butyl lactate, methylethylbenzoate).

The corrosion control composition can further comprise a kinetic hydrateinhibitor. The composition can comprise from about 0.1 wt-% to about 25wt-%, from about 0.5 wt-% to about 20 wt-%, from about 1 wt-% to about10 wt-%, from about 0.1 wt-% to about 10 wt-%, from about 0.5 wt-% toabout 5 wt-%, or from about 0.5 wt-% to about 4 wt-% of a kinetichydrate inhibitor, based on total weight of the composition. Suitablekinetic hydrate inhibitors and anti-agglomerates include, but are notlimited to, polymers and copolymers, polysaccharides (such ashydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), starch,starch derivatives, and xanthan), lactams (such as polyvinylcaprolactam,polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidone ofvarious molecular weights), fatty acid salts, ethoxylated alcohols,propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters,polyglycerol esters of fatty acids, alkyl glucosides, alkylpolyglucosides, alkyl sulfates, alkyl sulfonates, alkyl estersulfonates, alkyl aromatic sulfonates, alkyl betaine, alkyl amidobetaines, hydrocarbon based dispersants (such as lignosulfonates,iminodisuccinates, polyaspartates), amino acids, and proteins.

The corrosion control composition can further comprise a pH modifier.The composition can comprise from about 0.1 wt-% to about 20 wt-%, fromabout 0.5 wt-% to about 10 wt-%, or from about 0.5 wt-% to about 5 wt-%of a pH modifier, based on total weight of the composition. Suitable pHmodifiers include, but are not limited to, alkali hydroxides, alkalicarbonates, alkali bicarbonates, alkaline earth metal hydroxides,alkaline earth metal carbonates, alkaline earth metal bicarbonates andmixtures or combinations thereof. Exemplary pH modifiers include sodiumhydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodiumcarbonate, potassium carbonate, sodium bicarbonate, potassiumbicarbonate, magnesium oxide, and magnesium hydroxide.

The corrosion control composition can further comprise a surfactant. Thecomposition can comprise from about 0.1 wt-% to about 10 wt-%, fromabout 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% to about 4 wt-%of a surfactant, based on total weight of the composition. A suitablesurfactant can be a nonionic, semi-nonionic, cationic, anionic,amphoteric, zwitterionic, Gemini, di-cationic, di-anionic surfactant, ormixtures thereof. Anionic surfactants include alkyl aryl sulfonates,olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ethersulfates, alkyl carboxylates and alkyl ether carboxylates, and alkyl andethoxylated alkyl phosphate esters, and mono and dialkyl sulfosuccinatesand sulfosuccinamates. Nonionic surfactants include alcohol alkoxylates,alkylphenol alkoxylates, block copolymers of ethylene, block copolymersof ethylene and propylene, propylene and butylene oxides, alkyl dimethylamine oxides, alkyl-bis(2-hydroxyethyl) amine oxides, alkyl amidopropyldimethyl amine oxides, alkylamidopropyl-bis(2-hydroxyethyl) amineoxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitanesters and polyalkoxylated sorbitan esters, and alkoyl polyethyleneglycol esters and diesters. Also included are betaines and sultanes,amphoteric surfactants such as alkyl amphoacetates and amphodiacetates,alkyl amphopropionates and amphodipropionates, andalkyliminodipropionate.

In some embodiments, the surfactant is phosphate esters of ethoxylatedC10-C16 alcohols, ethoxylated C11-C14 iso or C13 rich phosphates,ethoxylated nonylphenol, ethoxylated branched nonylphenol, or mixturethereof.

The corrosion control composition can further comprise other additionalcorrosion control composition agents that provide a functional and/orbeneficial property. For example, additional corrosion controlcomposition agent can be a sequestrant, solubilizer, lubricant, buffer,cleaning agent, rinse aid, preservative, binder, thickener or otherviscosity modifier, processing aid, water-conditioning agent, foaminhibitor or foam generator, threshold agent or system, aestheticenhancing agent (e.g., dye, odorant, perfume), or other agentd suitablefor formulation with the corrosion inhibitor composition, and mixturesthereof. Additional agents vary according to the specific corrosioncontrol composition being manufactured and its intend use as one skilledin the art will appreciate.

Alternatively, the corrosion control composition does not contain or isfree of any of the additional corrosion control composition agents.

Additionally, the corrosion control composition can be formulated intoexemplary compositions comprising the following components as shown inTable 1. These formulations include the ranges of the components listedand can optionally include additional corrosion control compositionagents. The values in the Table 1 below are weight percentages.

TABLE 1 Exemplary Corrosion Control Compositions Component 1 2 3 4 5 6 78 9 10 11 12 Di-cationic or 0.1-20 0.1-20 0.1-20   0.1-20 0.1-20 0.1-20   10-20  10-20 10-20  10-20  10-20 0.1-20 di-anionic compoundsCarrier  5-40 — 5-50 — 5-50 5-50   5-40 — 5-50 — —  10-20 additional0.1-20 0.1-20 — — — —  0.1-20  0.1-20 — — — 0.1-20 corrosion inhibitorOrganic sulfur 0.1-5  0.1-5  0.1-5   0.1-5 — — 0.1-5 0.1-5 0.1-5   — —0.1-5  compound Scale inhibitor  1-10  1-10 1-10   1-10 1-10 —   1-10  1-10 1-10 1-10 —  1-10 surfactant — — — — — — — — — — — 0.1-25 Biocide0.5-5  0.5-5  0.5-5   0.5-5 0.5-5   0.5-5   0.5-5 0.5-5 0.5-5   0.5-5  0.5-5  Water 0.00  0-40 0-10   0-60 0-15 0-25 0.00   0-40 0-10 0-65 0-75 Component 13 14 15 16 17 18 19 20 21 22 23 24 Di-cationic or0.1-20 0.1-20 0.1-20 0.1-20 0.1-20 0.1-20  10-20  10-20  10-20 10-20 10-20 10-20  di-anionic compounds carrier —  10-20 —  10-35  10-35 — 10-15 — — 10-35  10-35 — Additional 0.1-20 0.1-20 0.1-20 0.1-20 0.1-200.1-20 0.1-20 0.1-20 0.1-20 0.1-20  0.1-20 0.1-20  corrosion inhibitorOrganic sulfur 0.1-5  — — — — — 0.1-5  — — — — — compound Scaleinhibitor  1-10  1-10 — —  1-10 —  1-10  1-10 — — — 1-10 surfactant0.1-25 0.1-25 0.1-25 — — — 0.1-25 0.1-25 0.1-25 — 0.1-25 — Biocide — — —— — 0.5-5  0.5-5  0.5-5  0.5-5  0.5-5  — — Water  0-20  0-5  0-35  0-25 0-15  0-55 0.00  0-20  0-30  0-20 0.00 0-50Water System

The corrosion control composition or its use solution is applied to awater system to prevent corrosion on surfaces in the water system oronto surfaces within the water system. In some embodiments, the watersystem in the disclosed methods herein is an industrial water system. Inother embodiments, the water system can be, but is not limited to, acooling water system, including an open recirculating system, closed andonce-through cooling water system, boilers and boiler water system,petroleum well system, downhole formation, geothermal well, and otherwater system in oil and gas field applications, a mineral washingsystem, flotation and benefaction system, paper mill digester, washer,bleach plant, stock chest, white water system, paper machine surface,black liquor evaporator in the pulp industry, gas scrubber and airwasher, continuous casting processes in the metallurgical industry, airconditioning and refrigeration system, industrial and petroleum processwater, indirect contact cooling and heating water, water reclamationsystem, water purification system, membrane filtration water system,food processing stream (meat, vegetable, sugar beets, sugar cane, grain,poultry, fruit and soybean), waste treatment system, clarifier,liquid-solid application, municipal sewage treatment, municipal watersystem, potable water system, aquifer, water tank, sprinkler system, orwater heater.

The water system can be those used in oil and gas operations. The watersystem can comprise water, oil, and solid. In some embodiments, thewater system comprises mostly oil or hydrocarbons. For example, thewater systems include oil or gasoline in tanks or pipelines. In someembodiments, the water system is one used in oil and gas operations.

In some embodiments, the water system is a cooling water system,including open recirculating, closed and once-through cooling watersystem, paper machine surface, food processing stream, waste treatmentsystem, or potable water system.

Use of the Methods or Compositions Disclosed

In some embodiments, for the methods disclosed herein, providing acorrosion control composition into a water system means that thecorrosion control composition, one or more di-cationic or di-anioniccompounds, or a use solution thereof is added into a fluid comprisingwater or onto a surface of a water system. In other embodiments,providing a corrosion control composition into a water system meansadding the corrosion control composition or the di-cationic ordi-anionic compounds onto the surface or into the water of the watersystem. In some other embodiments, providing a corrosion controlcomposition into a water system means adding the corrosion controlcomposition, di-cationic or di-anionic compounds, or use solutionthereof to a fluid or gas that in turn contacts the surfaces of thewater system. The corrosion control composition, di-cationic ordi-anionic compounds, or use solution thereof may be added continuously,or intermittently when more compounds or compositions may be needed.

A use solution of a corrosion control composition or of one or moredi-cationic or di-anionic compounds as used herein refers to a dilutedsolution for the composition or compounds by a diluent. A diluent asused herein refers to water, the water of a water system, or one of thecarriers or solvents defined herein. The corrosion control compositionor the compounds can be diluted by a factor of 0.5, 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11-1,000,000, or any value there between to generate a usesolution and then provide the use solution to a water system or onto asurface. In this disclosure, when a composition or di-cationic ordi-anionic compounds are applied, either the composition/compounds oruse solution thereof is applied.

In some embodiments, the corrosion control composition or thedi-cationic or di-anionic compounds disclosed herein may be added to thewater of the water system, so the concentration of the composition orcompounds in the treated water system is in an concentration of fromabout 1 ppm to about 1000 ppm. In other embodiments, the amount of thecorrosion control composition or the di-cationic or di-anionic compoundsin the water of the water system may range from about 5 ppm to about 100ppm, about 5 ppm to about 50 ppm, about 5 ppm to about 40 ppm, about 5ppm to about 30 ppm, about 10 ppm to about 60 ppm, about 10 ppm to about50 ppm, about 10 ppm to about 40 ppm, about 10 ppm to about 30 ppm,about 20 ppm to about 60 ppm, about 20 ppm to about 50 ppm, about 20 ppmto about 40 ppm, or about 20 ppm to about 30 ppm. In some embodiments,the corrosion control composition or the di-cationic or di-anioniccompounds may be added to the water to an amount ranging from about 100ppm to about 1000 ppm, about 125 ppm to about 1000 ppm, about 250 ppm toabout 1000 ppm, or about 500 ppm to about 1000 ppm.

The corrosion control composition or the di-cationic or di-anioniccompounds can be used for corrosion control in oil and gas applicationssuch as by treating a gas or liquid stream with an effective amount ofthe compound or composition as described herein. The compounds andcompositions can be used in any industry where it is desirable toprevent corrosion at a surface.

The corrosion control composition or the di-cationic or di-anioniccompounds can be used in a condensate/oil systems/gas system, or anycombination thereof. For example, the corrosion control composition orthe di-cationic or di-anionic compounds can be used in corrosion controlon heat exchanger surfaces. The corrosion control composition or thedi-cationic or di-anionic compounds can be applied to a gas or liquidproduced, or used in the production, transportation, storage, and/orseparation of crude oil or natural gas. The corrosion controlcomposition or the di-cationic or di-anionic compounds can be applied toa gas stream used or produced in a coal-fired process, such as acoal-fired power plant.

The corrosion control composition or the di-cationic or di-anioniccompounds can be applied to a gas or liquid produced or used in awaste-water process, a farm, a slaughter house, a land-fill, amunicipality waste-water plant, a coking coal process, or a biofuelprocess.

A fluid to which the corrosion control composition or the di-cationic ordi-anionic compounds can be introduced can be an aqueous medium. Theaqueous medium can comprise water, gas, and optionally liquidhydrocarbon.

A fluid to which the corrosion control composition or the di-cationic ordi-anionic compounds can be introduced can be a liquid hydrocarbon. Theliquid hydrocarbon can be any type of liquid hydrocarbon including, butnot limited to, crude oil, heavy oil, processed residual oil, bituminousoil, coker oils, coker gas oils, fluid catalytic cracker feeds, gas oil,naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jetfuel, gasoline, and kerosene. The fluid or gas can be a refinedhydrocarbon product.

A fluid or gas treated with the corrosion control composition or thedi-cationic or di-anionic compounds can be at any selected temperature,such as ambient temperature or an elevated temperature. The fluid (e.g.,liquid hydrocarbon) or gas can be at a temperature of from about 40° C.to about 250° C. The fluid or gas can be at a temperature of from about−50° C. to about 300° C., from about 0° C. to about 200° C., from about10° C. to about 100° C., or from about 20° C. to about 90° C. The fluidor gas can be at a temperature of about 22° C., about 23° C., about 24°C., about 25° C., about 26° C., about 27° C., about 28° C., about 29°C., about 30° C., about 31° C., about 32° C., about 33° C., about 34°C., about 35° C., about 36° C., about 37° C., about 38° C., about 39°C., or about 40° C. The fluid or gas can be at a temperature of about85° C., about 86° C., about 87° C., about 88° C., about 89° C., about90° C., about 91° C., about 92° C., about 93° C., about 94° C., about95° C., about 96° C., about 97° C., about 98° C., about 99° C., or about100° C.

The corrosion control composition or the di-cationic or di-anioniccompounds can be added to a fluid (or water system) at various levels ofwater cut. For example, the water cut can be from 0% to 100%volume/volume (v/v), from 1% to 80% v/v, or from 1% to 60% v/v. Thefluid can be an aqueous medium that contains various levels of salinity.The fluid can have a salinity of 0% to 25%, about 1% to 24%, or about10% to 25% weight/weight (w/w) total dissolved solids (TDS).

The fluid or gas of a water system or the water of a water system, inwhich the corrosion control composition or the di-cationic or di-anioniccompounds are introduced, can be contained in and/or exposed to manytypes of apparatuses. For example, the fluid or gas can be contained inan apparatus that transports fluid or gas from one point to another,such as an oil and/or gas pipeline. The apparatus can be part of an oiland/or gas refinery, such as a pipeline, a separation vessel, adehydration unit, or a gas line. The fluid can be contained in and/orexposed to an apparatus used in oil extraction and/or production, suchas a wellhead. The apparatus can be part of a coal-fired power plant.The apparatus can be a scrubber (e.g., a wet flue gas desulfurizer, aspray dry absorber, a dry sorbent injector, a spray tower, a contact orbubble tower, or the like). The apparatus can be a cargo vessel, astorage vessel, a holding tank, or a pipeline connecting the tanks,vespels, or processing units.

The corrosion control composition or the di-cationic or di-anioniccompounds can be introduced into a fluid or gas of the water system byany appropriate method for ensuring dispersal through the fluid or gas.For examples, the corrosion control composition or the di-cationic ordi-anionic compounds can be added to the hydrocarbon fluid before thehydrocarbon fluid contacts the surface.

The corrosion control composition or the di-cationic or di-anioniccompounds can be added at a point in a flow line upstream from the pointat which corrosion control is desired. The corrosion control compositionor the di-cationic or di-anionic compounds can be injected usingmechanical equipment such as chemical injection pumps, piping tees,injection fittings, atomizers, quills, and the like.

The corrosion control composition or the di-cationic or di-anioniccompounds can be pumped into an oil and/or gas pipeline using anumbilical line. A capillary injection system can be used to deliver thecorrosion control composition or the di-cationic or di-anionic compoundsto a selected fluid.

A fluid to which the corrosion control composition or the di-cationic ordi-anionic compounds can be introduced can be an aqueous medium. Theaqueous medium can comprise water, gas, and optionally liquidhydrocarbon. A fluid to which the corrosion control composition or thedi-cationic or di-anionic compounds can be introduced can be a liquidhydrocarbon.

The corrosion control composition or the di-cationic or di-anioniccompounds can be introduced into a liquid and a mixture of severalliquids, a liquid and gas, liquid, solid, and gas. The corrosion controlcomposition or the di-cationic or di-anionic compounds can be injectedinto a gas stream as an aqueous or non-aqueous solution, mixture, orslurry.

The fluid or gas can be passed through an absorption tower comprisingthe corrosion control composition or the di-cationic or di-anioniccompounds.

The corrosion control composition or the di-cationic or di-anioniccompounds can be applied to a fluid or gas to provide any selectedconcentration. In practice, the corrosion control composition or thedi-cationic or di-anionic compounds are typically added to a flow lineto provide an effective treating dose of the corrosion controlcomposition or the di-cationic or di-anionic compounds from about 0.01ppm to about 5,000 ppm. The corrosion control composition or thedi-cationic or di-anionic compounds can be applied to a fluid or gas toprovide an active concentration of about 1 parts per million (ppm) toabout 1,000,000 ppm, about 1 parts per million (ppm) to about 100,000ppm, or about 10 ppm to about 75,000 ppm. The polymer salts/compositionscan be applied to a fluid to provide an actives concentration of about100 ppm to about 10,000 ppm, about 200 ppm to about 8,000 ppm, or about500 ppm to about 6,000 ppm. The actives concentration means theconcentration of corrosion control composition or the di-cationic ordi-anionic compounds.

The corrosion control composition or the di-cationic or di-anioniccompounds can be applied to a fluid or gas to provide an activeconcentration of about 0.1 ppm, about 0.5 ppm, about 1 ppm, about 2 ppm,about 5 ppm, about 10 ppm, about 20 ppm, about 100 ppm, about 200 ppm,about 500 ppm, or about 1,000 ppm in the treated fluid or gas, e.g., thetreated water system. The corrosion control composition or thedi-cationic or di-anionic compounds can be applied to a fluid or gas orwater system to provide an actives concentration of about 0.125 ppm,about 0.25 ppm, about 0.625 ppm, about 1 ppm, about 1.25 ppm, about 2.5ppm, about 5 ppm, about 10 ppm, or about 20 ppm in the treated fluid,gas, or water system. Each water system can have its own dose levelrequirements, and the effective dose level of the corrosion controlcomposition or the di-cationic or di-anionic compounds to sufficientlyreduce the rate of microbial or biofilm growth can vary with the watersystem in which it is used.

The corrosion control composition or the di-cationic or di-anioniccompounds can be applied continuously, in batch, or a combinationthereof. The corrosion control composition or the di-cationic ordi-anionic compounds dosing can be continuous. The corrosion controlcomposition or the di-cationic or di-anionic compounds dosing can beintermittent (e.g., batch treatment) or can be continuous/maintainedand/or intermittent.

Dosage rates for continuous treatments typically range from about 10 ppmto about 500 ppm, or about 10 ppm to about 200 ppm. Dosage rates forbatch treatments typically range from about 10 ppm to about 400,000 ppm,or about 10 ppm to about 20,000 ppm. The corrosion control compositionor the di-cationic or di-anionic compounds can be applied as a pill to apipeline, providing a high dose (e.g., 20,000 ppm) of the composition.

The flow rate of a flow line in which the corrosion control compositionor the di-cationic or di-anionic compounds is used can be between about0.1 feet per second and about 1,000 feet per second, or between about0.1 feet per second and about 50 feet per second. The corrosion controlcomposition or the di-cationic or di-anionic compounds can also beformulated with water to facilitate addition to the flow line.

A surface of a water system can be any surface that can make contact tothe water or vapor of the water of the water system in any way. Thesurface can be a part of a wellbore or equipment used in the production,transportation, storage, and/or separation of a fluid such as crude oilor natural gas.

More specifically, the surface can be a part of equipment used acoal-fired process, a waste-water process, a farm, a slaughter house, aland-fill, a municipality waste-water plant, a coking coal process, or abiofuel process. Preferably, the surface can be a part of equipment usedin the production of crude oil or natural gas.

The equipment can comprise a pipeline, a storage vessel, downholeinjection tubing, a flow line, or an injection line.

The corrosion control composition or the di-cationic or di-anioniccompounds are useful for prevention corrosion of containers, processingfacilities, or equipment in the food service or food processingindustries. The corrosion control composition or the di-cationic ordi-anionic compounds have particular value for use on food packagingmaterials and equipment, and especially for cold or hot asepticpackaging. Examples of process facilities in which the corrosion controlcomposition or the di-cationic or di-anionic compounds can be employedinclude a milk line dairy, a continuous brewing system, food processinglines such as pumpable food systems and beverage lines, ware washmachines, low temperature ware wash machines, dishware, bottle washers,bottle chillers, warmers, third sink washers, processing equipment suchas tanks, vats, lines, pumps and hoses (e.g., dairy processing equipmentfor processing milk, cheese, ice cream and other dairy products), andtransportation vehicles. The corrosion control composition or thedi-cationic or di-anionic compounds can be used to inhibit corrosion intanks, lines, pumps, and other equipment used for the manufacture andstorage of soft drink materials, and also used in the bottling orcontainers for the beverages.

The corrosion control composition or the di-cationic or di-anioniccompounds can also be used on or in other industrial equipment and inother industrial process streams such as heaters, cooling towers,boilers, retort waters, rinse waters, aseptic packaging wash waters, andthe like. The corrosion control composition or the di-cationic ordi-anionic compounds can be used to treat surfaces in recreationalwaters such as in pools, spas, recreational flumes and water slides,fountains, and the like.

The corrosion control composition or the di-cationic or di-anioniccompounds can be used to treat metal surfaces contacted with cleaners insurfaces found in janitorial and/or housekeeping applications, foodprocessing equipment and/or plant applications, and in laundryapplications. For example, washers, such as tunnel washers for washingtextiles, can be treated according to methods disclosed herein.

The corrosion control composition or the di-cationic or di-anioniccompounds can be used or applied in combination with low temperaturedish and/or warewash sanitizing final rinse, toilet bowl cleaners, andlaundry bleaches. The corrosion control composition or the di-cationicor di-anionic compounds can be used to treat metal surfaces, such asware, cleaned and/or sanitized with corrosive sources.

The corrosion control composition or the di-cationic or di-anioniccompounds can be dispensed in any suitable method generally known by oneskilled in the art. For example, a spray-type dispenser can be used. Aspray-type dispenser functions by impinging a water spray upon anexposed surface of a composition to dissolve a portion of thecomposition, and then immediately directing the concentrate solutionincluding the composition out of the dispenser to a storage reservoir ordirectly to a point of use.

The corrosion control composition or the di-cationic or di-anioniccompounds can be dispensed by immersing either intermittently orcontinuously in the water, fluid, or gas of the water system. Thecorrosion control composition or the di-cationic or di-anionic compoundscan then dissolve, for example, at a controlled or predetermined rate.The rate can be effective to maintain a concentration of the dissolvedcompounds or compositions that are effective for use according to themethods disclosed herein.

The corrosion control composition disclosed herein can comprise fromabout 10 wt-% to about 90 wt-% of the carrier, biocide, additionalcorrosion inhibitor, additional corrosion control composition agent, ora combination thereof and from about 10 wt-% to about 90 wt-% of one ormore di-cationic or di-anionic compounds, from about 20 wt-% to about 80wt-% of the carrier, biocide, additional corrosion inhibitor, additionalcorrosion control composition agent, or a combination thereof and fromabout 20 wt-% to about 80 wt-% of one or more di-cationic or di-anioniccompounds; from about 30 wt-% to about 70 wt-% of the carrier, biocide,additional corrosion inhibitor, additional corrosion control compositionagent, or a combination thereof and from about 30 wt-% to about 70 wt-%of the one or more di-cationic or di-anionic compounds, or from about 40wt-% to about 60 wt-% of the carrier, biocide, additional corrosioninhibitor, additional corrosion control composition agent, or acombination thereof and from about 40 to about 60 wt. % of the one ormore di-cationic or di-anionic compounds.

In one aspect, disclosed herein is a corrosion control composition, thecomposition comprises one or more compounds according to one of FormulaI, Formula II, Formula III and one or more additional corrosion controlcomposition agents,

wherein X is NH or O; R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is anunsubstituted or substituted, linear or branched C₁-C₃₀ alkyl, cyclicalkyl, alkenyl, or alkynyl group; Z is NH or O; R² is H, CH₃, or anunsubstituted, linear or branched C₂-C₁₀ alkyl, alkenyl, or alkynylgroup; m is an integer of 1 to 4; R³ is absent or an unsubstituted,linear C₁-C₃₀ alkylene group; Y is —N R⁴R⁵R⁶⁽⁺⁾; Y′ is —COOH, —SO₃H,—PO₃H, —OSO₃H, —OPO₃H, or a salt thereof; R^(2′) is H, CH₃, or anunsubstituted or substituted, linear or branched C₁-C₁₀ alkyl, alkenyl,alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; and R⁴, R⁵, and R⁶are independently a C₁-C₁₀ alkyl group, and wherein the corrosioncontrol composition mitigates corrosion on the surface in the watersystem.

In another aspect, disclosed herein is a method for inhibiting corrosionat a surface in a water system, the method comprises providing acorrosion control composition or a use solution of the corrosion controlcomposition into a water system to generate a treated water system oronto a surface of the water system, wherein the corrosion controlcomposition comprises one or more compounds according to one of FormulaI, Formula II, Formula III and one or more additional corrosion controlcomposition agents,

wherein X is NH or O; R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is anunsubstituted or substituted, linear or branched C₅-C₃₀ alkyl, cyclicalkyl, alkenyl, or alkynyl group; Z is NH or O; R² is H, CH₃, or anunsubstituted, linear or branched C₂-C₁₀ alkyl, alkenyl, or alkynylgroup; m is an integer of 1 to 4; R³ is absent or an unsubstituted,linear C₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H,—PO₃H, —OSO₃H, —OPO₃H, or a salt thereof; R^(2′) is H, CH₃, or anunsubstituted or substituted, linear or branched C₁-C₁₀ alkyl, alkenyl,alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; and R⁴, R⁵, and R⁶are independently a C₁-C₁₀ alkyl group, and wherein the corrosioncontrol composition mitigates corrosion on the surface in the watersystem.

In some embodiments, the corrosion control composition can mitigatecorrosion on a metal surface to about 280 mpy, about 265, about 250 mpy,about 225 mpy, about 200 mpy, about 175 mpy, about 150 mpy, about 175mpy, about 100 mpy, or any value there between, when the di-cation ordi-anionic compound is at about 2 ppm and corrosion rate is measured bya bubble test.

In some embodiments, the one or more compounds are one or more ofFormula I. In some other embodiments, the one or more compounds are oneor more of Formula II. In yet some other embodiments, the one or morecompounds are one or more of Formula III. In some other embodiments, theone or more compounds are one or more of Formula II and Formula III.

In some embodiments of the disclosed compounds herein, X is NH. In someother embodiments, X is O.

In some embodiments, R¹¹ is R¹. In some other embodiments, R¹¹ isR¹—Z—(CH₂)_(m)—. In some embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, and Z isNH. In some other embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, and Z is O. Inyet some other embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, Z is NH, m is 2.

In some embodiments, R² is H. In some embodiments, R² is CH₃. In yetsome other embodiments, R² is CH₃CH₃, CH₂CH₂CH₃, or CH(CH₃)₂.

In some embodiments, Y is —N R⁴R⁵R⁶⁽⁺⁾. In some other embodiments, Y is—N R⁴R⁵R⁶⁽⁺⁾, and R⁴, R⁵, and R⁶ are independently CH₃. In yet someother embodiments, Y is —N R⁴R⁵R⁶⁽⁺⁾, and R⁴ and R⁵, independently CH₃,and R⁶ is a C₂-C₁₂ aromatic alkyl. In some other embodiments, Y is —NR⁴R⁵R⁶⁽⁺⁾, and R⁴ and R⁵, independently CH₃, and R⁶ is —CH₂—C₆H₅.

In some embodiments, Y is —N R⁴R⁵R⁶⁽⁺⁾ and the counter ion for Y anynegative charged ion or species. In some other embodiments, the counterion for Y is chloride, bromide, fluoride, iodide, acetate, aluminate,cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate,carbonate, hydrogen carbonate, hydrogen oxalate, hydrogen sulfate,hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

In some embodiments, Y is —COOH or salt thereof. In some otherembodiments, Y is —SO₃H, —OSO₃H, or salt thereof. In yet some otherembodiments, Y is —PO₃H, —OPO₃H, or salt thereof. In some otherembodiments, Y is an acidic species or salt thereof.

In some embodiments, R³ is CH₂. In some other embodiments, R³ is CH₂CH₂.In other embodiments, R³ is C(CH₃)₂. In yet some other embodiments, R³is an unsubstituted, linear, and saturated C₂-C₁₀ alkylene group. Insome embodiments, R³ is an unsubstituted, linear, and unsaturated C₂-C₁₀alkylene group.

In some embodiments, R¹ is a linear C₅-C₃₀ alkyl, alkenyl, or alkynylgroup. In some other embodiments, R¹ is a branched C₅-C₃₀ alkyl,alkenyl, or alkynyl group. In yet some other embodiments, R¹ is a linearand saturated C₅-C₃₀ alkyl group. In some other embodiments, R¹ is abranched and saturated C₅-C₃₀ alkyl group.

In some embodiments, R¹ is a linear C₁-C₃₀ alkenyl group with one ormore double bonds. In some other embodiments, wherein R¹ is a branchedC₃-C₃₀ alkenyl group with one or more double bonds.

In some embodiments, R¹ is a linear C₃-C₃₀ alkynyl group with one ormore triple bonds. In some other embodiments, R¹ is a branched C₃-C₃₀alkynyl group With one or more triple bonds.

In some embodiments, R¹¹ is a linear and saturated C₁-C₂₀ alkyl group.In some other embodiments, R¹¹ is a trans C₃-C₂₀ alkenyl group with atleast one double bond. In some other embodiments, R¹¹ is a C₃-C₂₀alkenyl group with at least one double bond of trans configuration. Insome embodiments, R¹¹ is a cis C₃-C₂₀ alkenyl group with at least onedouble bond. In some other embodiments, R¹¹ is a C₃-C₂₀ alkenyl groupwith at least one double bond of cis configuration.

In some embodiments, R¹¹ is R¹—NH—CH₂CH₂CH₂ group and R¹ is a linear andsaturated C₆-C₂₀ alkyl, a trans alkenyl, or a cis alkenyl group.

In some other embodiments, R² is H, X is NH, R³ is CH₂CH₂, Y isCH₂—N⁺(CH₃)₃Cl⁻.

In some embodiments, the compound is a mixture of two or moredi-cationic or anionic compounds. In some other embodiments, thecompound is a single or mixture of di-cationic compounds. In some otherembodiments, the compound is a single or mixture of di-anioniccompounds. The two or more di-cationic or anionic compounds aredifferent from each other by molecular or average molecular weight,structure or combination thereof.

In some embodiments, the compound is a mixture of at least two differentdi-cationic compounds derived from the same primary amine and activatedolefin or from different primary amines and activated olefins.

In some embodiments, the compound is derived from a primary amine and(3-Acrylamidopropyl)trimethylammonium chloride (APTAC). In some otherembodiments, the compound is derived from a primary amine and[3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC).

In some embodiments, the compound is derived from a primary amine and aactivated olefin. In some embodiments, the activated olefin is(3-Acrylamidopropyl)trimethylammonium chloride (APTAC),[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ),N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt(DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium methylsulfate (DMAEA-MSQ), or 2-(acryloyloxy)-N,N,N-trimethylethanaminiumchloride (DMAEA-MSQ).

In some other embodiments, the activated olefin is(3-Acrylamidopropyl)trimethylammonium chloride (APTAC),[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), ormixture thereof.

In some other embodiments, the activated olefin is2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ),N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt(DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium methylsulfate (DMAEA-MSQ), 2-(acryloyloxy)-N,N,N-trimethylethanaminiumchloride (DMAEA-MSQ), or mixture thereof.

In In some embodiments, the compound is derived from a primary amine andan activated olefin. In some embodiments, the activated olefin isacrylic acid, methacrylic acid, itaconic acid, maleic acid,vinylsulfonic acid, vinylphosphonic acid, or mixture thereof.

In some other embodiments, the activated olefin is2-acrylamido-2-methylpropane sulfonic acid (AMPS),3-(allyloxy)-2-hydroxypropane-1-sulfonate, or mixture thereof.

In yet some other embodiments, when the activated olefin containsanionic group that can bear negative charge at an alkaline pH, thecounter positive ions for the negative charges include, but are notlimited to, alkali metal ions, Li⁺, Na⁺, K⁺, NH₄ ⁺, a quaternaryammonium ion, etc.

In some embodiments, the compound is soluble or dispersible in water orthe corrosion control composition.

In some embodiments, the corrosion control composition comprises acarrier, wherein the carrier is water, an organic solvent, or a mixturethereof.

In some embodiments, the corrosion control composition further comprisesan organic solvent. In some other embodiments, the corrosion controlcomposition further comprises an organic solvent and water.

In some embodiments, the organic solvent is an alcohol, a hydrocarbon, aketone, an ether, an alkylene glycol, a glycol ether, an amide, anitrile, a sulfoxide, an ester, or any combination thereof. In someother embodiments, the organic solvent is an alcohol, an alkyleneglycol, an alkyleneglycol alkyl ether, or a combination thereof. In yetsome embodiments, the organic solvent is methanol, ethanol, propanol,isopropanol, butanol, isobutanol, monoethyleneglycol, ethyleneglycolmonobutyl ether, or a combination thereof.

In some embodiments, the organic solvent is methanol, ethanol, propanol,isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol,2-butoxyethanol, methylene glycol, ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, diethyleneglycol monomethyl ether,diethylene glycol monoethyl ether, ethylene glycol monobutyl ether,ethylene glycol dibutyl ether, pentane, hexane, cyclohexane,methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene,heavy aromatic naphtha, cyclohexanone, diisobutylketone, diethyl ether,propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, amixture thereof with water, or any combination thereof.

In some embodiments, wherein the corrosion control composition furthercomprises one or more of additional corrosion inhibitors. In someembodiments, wherein the corrosion control composition further comprisesone or more of additional corrosion inhibitors and a carrier. In someembodiments, the corrosion inhibitor is an imidazoline compound, apyridinium compound, or a combination thereof.

In some embodiments, the corrosion control composition further comprisesa fouling control agent. In some embodiments, the fouling control agentis a single quat compound.

In some embodiments, the corrosion control composition further comprisesa biocide. In some embodiments, the corrosion control compositionfurther comprises a biocide and carrier. In some other embodiments, thecorrosion control composition further comprises a biocide, corrosioninhibitor, and carrier.

In some embodiments, the biocide is an oxidizing biocide. In some otherembodiments, the biocide is a non-oxidizing biocide. In some otherembodiments, the biocide is chlorine, hypochlorite, ClO₂, bromine,ozone, hydrogen peroxide, peracetic acid, peroxysulphate,peroxycarboxylic acid, peroxycarboxylic acid composition, or mixturethereof. In some other embodiments, the biocide is glutaraldehyde,dibromonitrilopropionamide, isothiazolone, terbutylazine, polymericbiguanide, methylene bisthiocyanate, tetrakis hydroxymethyl phosphoniumsulphate, and combination thereof.

In some embodiments, the corrosion control composition further comprisesan organic sulfur compound. In some other embodiments, wherein theorganic sulfur compound is a mercaptoalkyl alcohol, mercaptoacetic acid,thioglycolic acid, 3,3′-dithiodipropionic acid, sodium thiosulfate,thiourea, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammoniumthiosulfate, sodium thiocyanate, ammonium thiocyanate, sodiummetabisulfite, or a combination thereof.

In some embodiments, the corrosion control composition further comprisesan acid. In some embodiments, the corrosion control composition furthercomprises an inorganic acid, mineral acid, organic acid, or mixturethereof. In some embodiments, the corrosion control compositioncomprises from about 1 wt-% to about 20 wt-% of the acid.

In some embodiments, the acid is hydrochloric acid, hydrofluoric acid,citric acid, formic acid, acetic acid, or mixture thereof.

In some embodiments, the corrosion control composition further comprisesa hydrogen sulfide scavenger. In some other embodiments, the hydrogensulfide scavenger is an oxidant, inorganic peroxide, sodium peroxide,chlorine dioxide; a C₁-C₁₀ aldehyde, formaldehyde, glyoxal,glutaraldehyde, acrolein, or methacrolein, a triazine, monoethanolaminetriazine, monomethylamine triazine, or a mixture thereof.

In some embodiments, the corrosion control composition further comprisesa surfactant. In some embodiments, the corrosion control compositionfurther comprises a surfactant, biocide, and carrier.

In some embodiments, the surfactant is a nonionic, semi-nonionic,cationic, anionic, amphoteric, zwitterionic, Gemini, di-cationic,di-anionic surfactant, or mixtures thereof.

In some embodiments, the surfactant is an alkyl phenol, fatty acid, ormixture thereof.

In some embodiments, the corrosion control composition further comprisesan asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, a gashydrate inhibitor, a pH modifier, or any combination thereof.

In some embodiments, the corrosion control composition further comprisesan emulsion breaker, reverse emulsion breaker, coagulant/flocculantagent, a water clarifier, a dispersant, antioxidant, polymer degradationprevention agent, permeability modifier, foaming agent, antifoamingagent, emulsifying agent, scavenger agent for CO₂, and/or O₂, gellingagent, lubricant, friction reducing agent, salt, or mixture thereof.

In some embodiments, the corrosion control composition is a liquid, gel,or a mixture comprising liquid/gel and solid.

In some embodiments, the corrosion control composition or a use solutionthereof has a pH of from about 1 to about 11, from about 1 to about 3,from about 3 to about 5, from about 5 to about 7, from about 7 to about9, from about 9 to about 11, about 2, about 4, about 6, about 8, about10, or any value there between.

In some embodiments, the corrosion control composition comprises fromabout 10 wt-% to about 80 wt-% of a di-cationic compound or mixturethereof. In some other embodiments, the corrosion control compositioncomprise from about 10 wt-% to about 30 wt-%, from about 30 wt-% toabout 50 wt-%, from about 50 wt-% to about 70 wt-%; from about 10 wt-%to about 40 wt-%, from about 20 wt-% to about 50 wt-%; from about 30wt-% to about 60 wt-%; from about 40 wt-% to about 80 wt-%, about 15wt-%, about 25 wt-%, about 35 wt-%, about 45 wt-%, about 55 wt-%, about65 wt-%, about 75 wt-%, or any value there between of a di-cationiccompound or mixture thereof.

In some embodiments, the corrosion control composition comprises fromabout 20 wt-% to about 60 wt-% of a di-anionic compound or mixturethereof. In some other embodiments, the corrosion control compositioncomprise from about 10 wt-% to about 30 wt-%, from about 30 wt-% toabout 50 wt-%, from about 50 wt-% to about 70 wt-%; from about 10 wt-%to about 40 wt-%, from about 20 wt-% to about 50 wt-%; from about 30wt-% to about 60 wt-%; from about 40 wt-% to about 80 wt-%, about 15wt-%, about 25 wt-%, about 35 wt-%, about 45 wt-%, about 55 wt-%, about65 wt-%, about 75 wt-%, or any value there between of a di-anioniccompound or mixture thereof.

In some embodiments, the di-cationic or di-anionic compound or mixturethereof has a concentration of from about 1 ppm to about 1000 ppm in thetreated water system. In some embodiments, the di-cationic or di-anioniccompound or mixture thereof has a concentration of from about 1 ppm toabout 5 ppm, from about 5 ppm to about 10 ppm, from about 1 ppm to about10 ppm, from about 1 ppm to about 20 ppm, from about 1 ppm to about 25ppm, from about 5 ppm to about 15 ppm, from about 15 ppm to about 50ppm, from about 50 ppm to about 100 ppm, from about 100 ppm to about 200ppm, from about 200 ppm to about 300 ppm, from about 300 ppm to about400 ppm, from about 400 ppm to about 500 ppm, from about 500 ppm toabout 600 ppm, from about 600 ppm to about 700 ppm, from about 700 ppmto about 800 ppm, from about 800 ppm to about 900 ppm, or any valuethere between in the treated water system.

In some embodiments, the corrosion control composition is provided tothe water system independently, simultaneously, or sequentially with anadditional functional ingredient.

In some embodiments, the water system comprises fresh water, recycledwater, salt water, surface water, produced water, or mixture thereof. Insome embodiments, the water system comprises water, oil, and solid, asthose found in oil and gas operations. In some embodiments, the watersystem comprises water and hydrocarbon or oil.

In some embodiments, the water system is a cooling water system, boilerwater system, petroleum wells, downhole formations, geothermal wells,mineral washing, flotation and benefaction, papermaking, gas scrubbers,air washers, continuous casting processes in the metallurgical industry,air conditioning and refrigeration, water reclamation, waterpurification, membrane filtration, food processing, clarifiers,municipal sewage treatment, municipal water treatment, or potable watersystem.

In some embodiments, the corrosion control composition or di-cationic ordi-anionic compounds disclosed herein can prevent corrosion on a surfacein a water system as indicated by a bubble cell test described in theExamples section of this disclosure, when the treated water system has adi-cationic or di-anionic concentration of from about 1 ppm to about1,000 ppm, from about 1 to about 900 ppm, from about 1 ppm to about 800ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 600ppm, from about 1 ppm to about 500 ppm, from about 1 ppm to about 400ppm, from about 1 ppm to about 300 ppm, from about 1 ppm to about 250ppm, from about 1 ppm to about 200 ppm, from about 1 ppm to about 150ppm, from about 1 ppm to about 100 ppm, from about 1 ppm to about 50ppm, from about 1 ppm to about 25 ppm, from about 1 ppm to about 10 ppm,from about 0.5 ppm to about 2 ppm, about 950 ppm, about 850 ppm, about750 ppm, about 650 ppm, about 550 ppm, about 450 ppm, about 350, about250 ppm, about 150 ppm, about 50 ppm, about 25 ppm, about 10 ppm, about5 ppm, about 2 ppm, about 1 ppm, about 0.5 ppm, or any range or valuethere between, after dosing the water system with the di-cationic ordi-anionic, or the corrosion control composition.

As used herein, the term “substantially free”, “free” or “free of”refers to compositions completely lacking the component or having such asmall amount of the component that the component does not affect theperformance of the composition. The component may be present as animpurity or as a contaminant and shall be less than 0.5 wt-%. In anotherembodiment, the amount of the component is less than 0.1 wt-% and in yetanother embodiment, the amount of component is less than 0.01 wt-%.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods and compositions of the present disclosure may comprise,consist essentially of, or consist of the components and ingredients ofthe disclosed compositions or methods as well as other ingredientsdescribed herein. As used herein, “consisting essentially of” means thatthe methods and compositions may include additional steps, components oringredients, but only if the additional steps, components or ingredientsdo not materially alter the basic and novel characteristics of theclaimed methods and compositions.

Without being limited to a particular mechanism of action or definitionof structure and function of the compounds, the compounds disclosedherein have two hydrophilic groups associated with one hydrophobicgroup. Accordingly, the compounds disclosed herein have a ratio ofhydrophilic heads to hydrophobic tail of 2:1 as compared to both aconventional surfactant and Gemini surfactant, which exhibit a 1:1ratio. FIG. 1A, FIG. 1B and FIG. 1C show a representation of anexemplary compound disclosed herein (FIG. 1C), together with ones for aconventional (FIG. 1A) and Gemini surfactant (FIG. 1B).

EXAMPLES

Embodiments of the present disclosure are further defined in thefollowing non-limiting Examples. These Examples, while indicatingcertain embodiments of the disclosure, are given by way of illustrationonly. From the above discussion and these Examples, one skilled in theart can ascertain the essential characteristics of this disclosure, andwithout departing from the spirit and scope thereof, can make variouschanges and modifications of the embodiments of the disclosure to adaptit to various usages and conditions. Thus, various modifications of theembodiments of the disclosure, in addition to those shown and describedherein, will be apparent to those skilled in the art from the foregoingdescription. Such modifications are also intended to fall within thescope of the appended claims.

The following non-limiting examples are provided to further illustratevarious aspects of the present disclosure. All chemicals were used asreceived from the supplier unless otherwise noted.

NMR samples of the di-cationic compounds or salts thereof were preparedin D₂O. All spectra were acquired at 25° C. Quantitative proton (¹H) andcarbon (¹³C) were acquired using a single-pulse sequence implemented onan AGILENT 500 MHz spectrometer equipped with a 10 mm broad-band probefor carbon or a 5 mm two-channel probe for proton with Z-gradient. ¹Hspectra were acquired with 4-8 scans. ¹³C spectra were acquired with400-500 scans. Data were processed and analyzed using MestReNova v. 9(Mestrelab, Spain).

The chemical shifts (ppm) are reported relative to TMS(tetramethylsilane) using the residual solvent peak as reference unlessotherwise noted. The following abbreviations are used to express themultiplicities: s=singlet; d=doublet; t=triplet; q=quartet; m=multiplet;br=broad.

Mass spectroscopy of the di-cationic compound(s) was conducted on a QEXACTIVE ORBITRAP high resolution mass spectrometer (Thermo FisherScientific) equipped with a quadrupole as an ion filter and with anelectrospray ionization (ESI) source. The di-cationic compound sampleswere diluted to about 100 ppm and then injected into the massspectrometer by infusion at the flow rate of 10 μL/minute. Spectra wereacquired in positive ESI mode; scan range: 50-750 m/z; resolution: 140k; AGC target: 36; sheath gas flow rate: 2 (arbitrary unit); auxiliarygas flow rate: 0 (arbitrary unit); spray voltage: 2.5 kV; capillarytemperature: 150° C.; auxiliary gas heater temperature: 30° C.; andS-Len RF level: 50. Data were acquired and analyzed by XCALIBUR andFREESTYLE software (Thermo Fisher Scientific).

Example 1

General Scheme to Synthesize Exemplary Compounds Containing TwoQuaternary Groups:

Exemplary di-cationic compounds containing two quat groups as disclosedherein and in Example Section were synthesized, by aza Michael additionreaction between a primary amine (1 mole) and α,β-unsaturated carbonylcompound containing at least one quat group (at least 2 moles). Thegeneric synthesis reaction scheme for preparation of the di-cationiccompounds disclosed herein is shown in FIG. 2.

In FIG. 2, R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is an unsubstituted orsubstituted, linear or branched C₅-C₃₀ alkyl, cyclic alkyl, alkenyl, oralkynyl group; Z is NH or O; R² is H, CH₃, or an unsubstituted, linearor branched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; m is an integer of1 to 4; and n is an integer of 1-20.

The reaction shown in FIG. 2 can be carried out in water at 80° C. Theprogression of this reaction can be monitored by ESI-MS and/or NMRspectroscopy for consumption of the monomer. The reaction can be stoppedat time when a yield of about 98% for the diquat product had obtained.For reactions that proceeded to completion, the formed product can beseparated by removal of solvent or by precipitation in a non-polarsolvent that was the opposite of the reaction media. For the reactionsin water, the formed product is precipitated from the aqueous reactionmixture. Higher pressure can speed-up the reaction. The compounds I-VIin the following Examples were made according to this generic scheme,but using different reactants as set forth in further detailed in eachExample.

Example 2 Synthesis of3,3′-((3,3′-(octylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (I)

In this Example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 30 grams, 0.10 mol) was charged into a 250-mL three-necked roundbottom flask (RBF) equipped with an overhead stirrer, temperature probe,and condenser. Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005mol) and water (41 g) were added into the flask. Octylamine (7 grams,99%, 0.053 mol) was then added portion wise to the well-stirred reactionmixture. The resulting suspension was stirred at 80° C. overnight. Asthe reaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜37 wt %) aqueous solution of thediquat compound was stored in the container. Mass spectrometry (+ESI-MS)confirmed synthesis of the diquat compound I: calc. [M-2Cl⁻]²⁺ 235.73,found 235.7241; calc. [M-Cl⁻]⁺ 506.42, found 506.4182.

Example 3 Synthesis of 3,3′-((3,3′-(dodecylazanedyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (II)

In this example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 30 grams, 0.10 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005 mol) and water(63 g) were added into the flask. Dodecylamine (10 grams, 98%, 0.053mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜31 wt %) aqueous solution of thediquat compound II was used as is. Mass spectrometry (+ESI-MS) confirmedsynthesis of diquat compound II: calc. [M-2Cl⁻]²⁺ 263.76, found263.7554; calc. [M-Cl⁻]⁺ 562.48, found 562.4806.

Example 4 Synthesis of3,3′-((3,3′-(hexadecylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (III)

In this example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 41 grams, 0.149 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005 mol) and water(100 g) were added into the flask. Hexadecylamine (20 grams, 90%, 0.0745mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜30 wt %) aqueous solution of thediquat compound III was used as is. Mass spectrometry (+ESI/MS)confirmed synthesis of diquat compound III: calc. [M-2Cl⁻]²⁺ 291.79,found 291.7870; calc. [M-Cl⁻]⁺ 618.54, found 618.5439.

Example 5 Synthesis of3,3′-((3,3′-(octylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (IV)

In this example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 40 grams, 0.145 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005 mol) and water(100 g) were added into the flask. Octadecylamine (20 grams, 98%, 0.072mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜31 wt %) aqueous solution of thediquat compound IV was used as is. Mass spectrometry (+ESI-MS) confirmedsynthesis of the diquat compound IV: calc. [M-2Cl⁻]²⁺ 305.80, found305.8014; calc. [M-Cl⁻]⁺ 646.58, found 648.5791.

Example 6 Synthesis of 3,3′-((3,3′-(octadec-9-en-1-ylazanediyl)bis(propanoyl)) bis(azanediyl)) bis(N,N,N-trimethylpropan-1-aminium)chloride (V)

In this example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 30 grams, 0.109 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.25 grams, 10%, 0.0001 mol) andwater (70 g) were added into the flask. Oleylamine (15 grams, 95%, 0.053mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜32 wt %) aqueous solution of thediquat compound V was used as is. Mass spectrometry (+ESI-MS) confirmedsynthesis of the diquat compound V: calc. [M-2Cl⁻]²⁺ 304.80, found304.7949; calc. [M-Cl⁻]⁺ 644.56, found 644.5596.

Example 7 Synthesis of3,3′-((3,3′-((3-(octadec-9-en-1-yl-amino)propyl)azanediyl)bis(propanoyl))bis(azanediyl)) bis(N,N,N-trimethylpropan-1-aminium) chloride (VI)

In this example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 42 grams, 0.152 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.25 grams, 10%, 0.0001 mol) andwater (130 g) were added into the flask. N-oleylpropanediamine (25grams, 99%, 0.076 mol) was then added portion wise to the well-stirredreaction mixture. The resulting suspension was stirred at 80° C.overnight. As the reaction proceeded to completion, the suspensionturned into a clear yellowish solution. The resulting (˜28 wt %) aqueoussolution of the diquat compound VI was used as is. Mass spectrometry(+ESI/MS) confirmed synthesis of diquat compound VI: calc. [M-2Cl⁻]²⁺333.32, found 333.3238; calc. [M-Cl⁻]⁺ 701.62, found 701.6173.

Example 8

Corrosion Control Efficacy of Some Exemplary Di-Cationic Compounds

In this Example, some exemplary di-cationic compounds were tested fortheir efficacy to prevent corrosion. The tested samples were madeaccording to the reaction presented in Example 1 and listed in thefollowing Table 2. The precursor primary amine for each compound islisted and the other reactant to produce the listed samples is(3-acrylamidopropyl) trimethylammonium chloride.

TABLE 2 List of the exemplary compounds for corrosion control test.Sample ID: Chemistry AMINE (R—NH₂) 1 HEXADECYLAMINE 2 OCTADECYLAMINE 3OLEYLAMINE 4 N-OLEYLPROPANEDIAMINE 5 OCTYLAMINE 6 DODECYLAMINE 7CORSAMINE DT 8 CORSAMINE TRT

The efficacy for corrosion control is usually measured by corrosionbubble cell tests. The bubble test simulates low flow areas where littleor no mixing of water and oil occurs. The test was conducted in fluidscontaining 80% brine (3% sodium chloride) and 20% hydrocarbon (75%LVT-200 and 25% xylene). The fluids were placed into kettles and purgedwith carbon dioxide. The brine was placed into kettles and purged withcarbon dioxide. The brine was continually purged with carbon dioxide tosaturate the brine prior to starting the test. After the test began, thetest cell was blanketed with carbon dioxide one hour prior to electrodeinsertion and through the duration of the test to maintain saturation.The kettles were stirred at 150 revolutions per minute (rpm) for theduration of the test to maintain thermal equilibrium at 80° C. Thecorrosion rate was measured by Linear Polarization Resistance (LPR)techniques. The working electrode used was 1018 carbon steel. Thecounter and reference electrodes were both Hastelloy. The electrodeswere all cleaned and polished prior to testing. Data were collected forthree hours before 20 ppm of each of the compositions (containing 2 ppmof each of various di-cationic compounds or salts thereof or the controlC₁₂-C₁₈ alkyl dimethyl benzyl ammonium chloride and 1% 2-mercaptoethanol(2ME) as synergist in an organic solvent) was dosed into its respectivecell. Data were collected overnight.

The control compounds for this Example are commonly used benzyl ammoniumchloride quaternary chemistry and imidazoline chemistry, respectively.

The results of the bubble test are shown in FIG. 3 and Table 3, whereinppm is parts per million, CI is corrosion inhibitor, and mpy is mils peryear. 0.2 ppm of 2-mercaptoethanol (2ME) were present with each testeddi-cationic compound or control. FIG. 3 shows the corrosion rate in milsper year during the bubble test period (18 hour). For the blank sample,no 2-mercaptoethanol (2ME) was added.

TABLE 3 Corrosion rate at 15th Hour after Di-cationic compound orcontrol compound addition in bubble test results Inhibited CorrosionDosage of Rate 15 h Cationic After Di- Di-cationic Salt Polymer cationicSalt or Control Salt or or Control Cationic Compound Addition % Compound(ppm) (mpy) Protection Blank 0 500 −92 C₁₂-C₁₈ alkyl 2 339 32 dimethylbenzyl ammonium chloride (Control 1) TOFA:DETA 2 432 14 imidazolinesalted with acetic acid (Control 2) 1 2 235 53 2 2 264 47 3 2 239 52 4 2232 54 5 2 206 59 6 2 258 48 7 2 318 36 8 2 220 88

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims.

What is claimed is:
 1. A method of for inhibiting corrosion at a surfacein a water system comprising: providing a corrosion control compositionor a use solution of the corrosion control composition into a watersystem to generate a treated water system or onto to a surface of thewater system, wherein the corrosion control composition comprises one ormore compounds according to one of Formula I, Formula II, Formula IIIand one or more additional corrosion control composition agents,

wherein: X is NH or O; R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is anunsubstituted or substituted, linear or branched C₅-C₃₀ alkyl, cyclicalkyl, alkenyl, or alkynyl group; Z is NH or O; R² is H, CH₃, or anunsubstituted, linear or branched C₂-C₁₀ alkyl, alkenyl, or alkynylgroup; m is an integer of 1 to 4; R³ is absent or an unsubstituted,linear C₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H,—PO₃H, —OSO₃H, —OPO₃H, or a salt thereof; and R⁴, R⁵, and R⁶ areindependently a C₁-C₁₀ alkyl group; R^(2′) is H, CH₃, or anunsubstituted or substituted, linear or branched C₁-C₁₀ alkyl, alkenyl,alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′ and wherein thecorrosion control composition mitigates corrosion on the surface in thewater system.
 2. The method according to claim 1, wherein X is NH. 3.The method according to claim 1, wherein X is O.
 4. The method accordingto claim 1, wherein R¹¹ is R¹ and R¹ is a linear C₅-C₃₀ alkyl, alkenyl,or alkynyl group.
 5. The method according to claim 1, wherein R¹¹ isR¹—Z—(CH₂)_(m)— or R¹—Z—(CH₂)₂—, Z is NH, and R¹ is a linear C₅-C₃₀alkyl, alkenyl, or alkynyl group.
 6. The method according to claim 1,wherein R¹¹ is R¹—Z—(CH₂)_(m)—, Z is O, and R¹ is a linear C₅-C₃₀ alkyl,alkenyl, or alkynyl group.
 7. The method according to claim 1, whereinR² is H or CH₃.
 8. The method according to claim 1, wherein Y is—NR⁴R⁵R⁶⁽⁺⁾, N(CH₃)₃ ⁺, N(CH₃)₂R₆ ⁺, and wherein R⁶ is a C₂-C₁₂ alkyl,aryl, or is —CH₂—C₆H₅.
 9. The method according to claim 1, wherein R³ isCH₂, CH₂CH₂, or C(CH₃)₂, an unsubstituted and linear C₂-C₁₀ alkylenegroup.
 10. The method according to claim 1, wherein R¹¹ is a C₆-C₂₀alkenyl group with at least one trans or cis double bond.
 11. The methodaccording to claim 1, wherein the corrosion control composition agent isa carrier, wherein the carrier is water, an organic solvent, or amixture thereof.
 12. The method according to claim 1, wherein thecorrosion control composition agent is a carrier and one or moreadditional corrosion inhibitors.
 13. The method according to claim 1,wherein the corrosion control composition agent is a biocide, whereinthe biocide is chlorine, hypochlorite, ClO₂, bromine, ozone, hydrogenperoxide, peracetic acid, peroxycarboxylic acid composition,peroxysulphate, glutaraldehyde, dibromonitrilopropionamide,isothiazolone, terbutylazine, polymeric biguanide, methylenebisthiocyanate, tetrakis hydroxymethyl phosphonium sulphate, or anycombination thereof.
 14. The method according to claim 1, wherein thecorrosion control composition agent is an acid and wherein the corrosioncontrol composition comprises from about 1 wt-% to about 20 wt-% of theacid, wherein the acid is hydrochloric acid, hydrofluoric acid, citricacid, formic acid, acetic acid, or a mixture thereof.
 15. The methodaccording to claim 1, wherein the corrosion control composition agent isa surfactant.
 16. The method according to claim 1, wherein the corrosioncontrol composition agent is a scale inhibitor, gas hydrate inhibitor,pH modifier, or any combination thereof.
 17. The method according toclaim 1, wherein the corrosion control composition agent is an emulsionbreaker, reverse emulsion breaker, a fouling control agent,coagulant/flocculant agent, an emulsifier, a water clarifier, adispersant, antioxidant, polymer degradation prevention agent,permeability modifier, foaming agent, antifoaming agent, emulsifyingagent, scavenger agent for CO₂, and/or O₂, gelling agent, lubricant,friction reducing agent, salt, or mixture thereof.
 18. The methodaccording to claim 1, wherein the corrosion control composition is aliquid, gel, or a mixture comprising liquid/gel and solid.
 19. Themethod according to claim 1, wherein the corrosion control compositionor a use solution thereof has a pH of from about 1 to about
 11. 20. Themethod according to claim 1, wherein the corrosion control compositioncomprises from about 10 wt-% to about 80 wt-% of the compound.
 21. Themethod according to claim 1, wherein the compound has a concentration offrom about 1 ppm to about 1000 ppm in the treated water system.
 22. Themethod according to claim 1, wherein the water system comprises freshwater, recycled water, salt water, surface water, produced water, oil,hydrocarbon, or mixture thereof.
 23. The method according to claim 1,wherein the water system is a cooling water system, boiler water system,water system in oil and gas operations, in a petroleum well, downholeformation, geothermal well, mineral washing, flotation and benefaction,papermaking, gas scrubber, air washer, continuous casting processes inthe metallurgical industry, air conditioning and refrigeration, waterreclamation, water purification, membrane filtration, food processing,clarifiers, municipal sewage treatment, municipal water treatment, orpotable water system.
 24. A corrosion control composition comprising oneor more compounds according to one of Formula I, Formula II, and FormulaIII and one or more additional corrosion control composition agents,

wherein: X is NH or O; R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is anunsubstituted or substituted, linear or branched C₅-C₃₀ alkyl, cyclicalkyl, alkenyl, or alkynyl group; Z is NH or O; R² is H, CH₃, or anunsubstituted, linear or branched C₂-C₁₀ alkyl, alkenyl, or alkynylgroup; m is an integer of 1 to 4; R³ is absent or an unsubstituted,linear C₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H,—PO₃H, —OSO₃H, —OPO₃H, or a salt thereof; R⁴, R⁵, and R⁶ areindependently a C₁-C₁₀ alkyl group; R^(2′) is H, CH₃, or anunsubstituted or substituted, linear or branched C₁-C₁₀ alkyl, alkenyl,alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′, and wherein thecorrosion control composition mitigates corrosion on the surface in thewater system.